CN101296965A

CN101296965A - Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom

Info

Publication number: CN101296965A
Application number: CNA2006800401814A
Authority: CN
Inventors: E·D·克劳福德; T·J·佩科里尼; D·S·麦克威廉斯; D·S·波特; G·W·康奈尔; T·C·格姆罗思; B·F·巴顿; D·B·沙克福德
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-10-28
Filing date: 2006-10-27
Publication date: 2008-10-29
Also published as: CN101296966A; CN101346427A

Abstract

Described are polyester compositions comprising (a) a dicarboxylicacidcomponent comprising terephthalic acid residues; optionally, aromatic dicarboxylic acid or aliphatic dicarboxylic acid residues; minimal amounts of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; ethylene glycol, and optionally, cyclohexanedimethanol residues.

Description

Polymer blend that comprises cyclobutanediol and goods prepared therefrom with certain combination of logarithmic viscosity number and medium second-order transition temperature

The cross reference of related application

[001] the application requires the right of priority of following application according to 35U.S.C. § 119 (e): the U.S. Provisional Application sequence number 60/731,454 that on October 28th, 2005 submitted to; The U.S. Provisional Application sequence number 60/731,389 that on October 28th, 2005 submitted to; The U.S. Provisional Application sequence number 60/739,058 that on November 22nd, 2005 submitted to; The U.S. Provisional Application sequence number 60/738,869 that on November 22nd, 2005 submitted to; The U.S. Provisional Application sequence number 60/750,692 that on December 15th, 2005 submitted to; The U.S. Provisional Application sequence number 60/750,693 that on December 15th, 2005 submitted to; The U.S. Provisional Application sequence number 60/750,682 that on December 15th, 2005 submitted to; With the U.S. Provisional Application sequence number of submitting on December 15th, 2,005 60/750,547; The U. S. application sequence number 110/390,672 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,752 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,794 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,565 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,671 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,853 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,631 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,655 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,125 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,751 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,955 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,827 that on March 28th, 2006 submitted to; The U. S. application sequence number 60/786,572 that on March 28th, 2006 submitted to; The U. S. application sequence number 60/786,596 that on March 28th, 2006 submitted to; The U. S. application sequence number 60/786,547 that on March 28th, 2006 submitted to; The U. S. application sequence number 60/786,571 that on March 28th, 2006 submitted to; The U. S. application sequence number 60/786,598 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,883 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,846 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,809 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,812 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,124 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,908 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,793 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,642 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,826 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,563 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,847 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,156 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,630 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,495 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,576 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,858 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,629 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,485 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,811 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,750 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,773 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,865 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,654 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,882 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,836 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,063 that on March 28th, 2006 submitted to; The U. S. application sequence number that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,814 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,722 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,659 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,137 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,505 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/390,864 that on March 28th, 2006 submitted to; The U. S. application sequence number 11/391,571 that on March 28th, 2006 submitted to is incorporated herein its full content as a reference.

Invention field

[002] generality of the present invention relates to by terephthalic acid or its ester or its mixture; 2,2,4,4-tetramethyl--1,3-cyclobutanediol; With the polymer blend of cyclohexanedimethanol preparation, this polyester has certain combination of logarithmic viscosity number and second-order transition temperature (Tg).These compositions have high impact, medium second-order transition temperature (Tg), toughness, some logarithmic viscosity number, low ductile-brittle transition temperature, good color and certain combination of at least two kinds of transparency, low density, chemical resistant properties and long hypocrystalline time, and they are configured as goods easily this permission.

Background of invention

[003] poly-(terephthalic acid 1,4-hexanaphthene dimethyl ester) (PCT), a kind of only based on the polyester of terephthalic acid or its ester and 1,4 cyclohexane dimethanol, be known in this area and have commercially available.This polyester is rapid crystallization when being cooled off by melt, makes to form very difficulty of amorphous goods by methods known in the art such as extrusion molding, injection moulding etc.For the crystallization rate of the PCT that slows down, can prepare the copolyesters that comprises other dicarboxylic acid or glycol such as m-phthalic acid or ethylene glycol.The PCT of these ethylene glycol or isophthalate modified also is known in this area and has commercially available.

[004] a kind ofly is used to produce the common copolyesters of film, thin plate and moulded product by terephthalic acid, 1,4 cyclohexane dimethanol and ethylene glycol.Though these copolyesters are useful in many end-uses field, when comprising enough modification ethylene glycol to provide long hypocrystalline during the time in prescription, they are demonstrating defective such as second-order transition temperature and shock strength aspect of performance.For example, by terephthalic acid, 1, the copolyesters with sufficiently long hypocrystalline time of 4-cyclohexanedimethanol and ethylene glycol can provide amorphous products, and this product demonstration it is believed that than undesirable higher ductile-brittle transition temperature of composition disclosed here and lower second-order transition temperature.

[005] 4, the polycarbonate of 4 '-isopropylidene biphenol (bisphenol-a polycarbonate) has been used as polyester substitute known in the art and has been well-known engineering moulded plastic.Bisphenol-a polycarbonate is transparent high performance plastics, and it has good physicals, for example dimensional stability, high heat resistance and good shock strength.Although bisphenol-a polycarbonate has many good physicalies, its higher melt viscosity causes the melt processable of difference, and this polycarbonate shows the chemical resistant properties of difference.It also is difficult to thermoforming.

[006] comprise 2,2,4,4-tetramethyl--1, the polymkeric substance of 3-cyclobutanediol have also carried out general description in the art.Yet these polymkeric substance show high logarithmic viscosity number, high melt viscosity and high second-order transition temperature usually, make that the equipment that is used for industry is not enough to make or post polymerization is processed these materials.

[007] therefore, this area need have two or more performance combination of polymers that is selected from least a following performance: the toughness of polyester, medium second-order transition temperature (Tg), good shock strength, stability to hydrolysis, chemical resistant properties, long hypocrystalline time, low ductile-brittle transition temperature, good color and transparency, lower density and/or hot formability remain on the workability on the standard equipment that is used for industry simultaneously.

Summary of the invention

[008] it is believed that by terephthalic acid residue or its ester or its mixture; Cyclohexanedimethanol or its ester or its mixture; With 2,2,4,4-tetramethyl--1, some composition of certain combination with logarithmic viscosity number and/or second-order transition temperature of 3-cyclobutanediol residue preparation, with regard at least a following performance: with regard to high impact, stability to hydrolysis, toughness, chemical resistant properties, good color and transparency, long hypocrystalline time, low ductile-brittle transition temperature, the lower proportion and hot formability, more superior than polyester known in the art and polycarbonate.These compositions it is believed that aspect thermotolerance similar with polycarbonate, and remain machinable on standard industry equipment.

[009] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

Ii) 0-30mol%'s has an aromatic dicarboxylic acid residue of 20 carbon atoms at the most; With

Iii) 0-10mol%'s has an aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; With

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-99mol%,

Wherein total mol% of dicarboxylic acid component is that total mol% of 100mol% and diol component is 100mol%; With

Wherein the concentration with 0.25g/50ml is that 0.10-is less than 1.0dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 85-120 ℃ Tg.

[010] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-99mol%,

Wherein the concentration with 0.25g/50ml is that 0.35-is less than 1.0dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 85-120 ℃ Tg.

[011] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 5-is less than 2,2,4 of 50mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein the concentration with 0.25g/50ml is 0.50-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 85-125 ℃ Tg.

[012] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester has 85-120 ℃ Tg.

[013] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 85-120 ℃ Tg.

[014] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 85-120 ℃ Tg.

[015] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein the concentration with 0.25g/50ml is 0.50-0.8dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 85-120 ℃ Tg.

[016] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein the concentration with 0.25g/50ml is 0.50-0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 85-120 ℃ Tg.

[017] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-99mol%,

Wherein the concentration with 0.25g/50ml is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; And

Wherein said polyester has 100-120 ℃ Tg.

[018] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 100-120 ℃ Tg.

[019] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 100-120 ℃ Tg.

[020] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.50-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 95-115 ℃ Tg.

[021] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 95-115 ℃ Tg.

[022] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 95-115 ℃ Tg.

[023] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.50-0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-125 ℃ Tg.

[024] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is that 0.50-is less than 0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-120 ℃ Tg.

[025] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester has 85-120 ℃ Tg.

[026] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.6-0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-120 ℃ Tg.

[027] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.65-0.75dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-120 ℃ Tg.

[028] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.68-0.78dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-120 ℃ Tg.

[029] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 85-120 ℃ Tg.

[030] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 85-120 ℃ Tg.

[031] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 85-120 ℃ Tg.

[032] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 85-120 ℃ Tg.

[033] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 17-28mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 72-83mol%,

Wherein said polyester has 85-120 ℃ Tg.

[034] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 100-120 ℃ Tg.

[035] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 17-28mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 72-83mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.7-0.8dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-120 ℃ Tg.

[036] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 17-28mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 72-83mol%,

Wherein said polyester has 100-120 ℃ Tg.

[037] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 17-28mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 100-115 ℃ Tg.

[038] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester has 95-115 ℃ Tg.

[039] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

Ii) greater than the cyclohexanedimethanol residue of 50-95mol%,

Wherein said polyester has 95-115 ℃ Tg.

[040] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 95-115 ℃ Tg.

[041] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%,

Wherein said polyester has 95-115 ℃ Tg.

[042] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 95-115 ℃ Tg.

[043] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester has 95-115 ℃ Tg.

[044] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-25mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 75-85mol%,

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.60-0.72dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 95-115 ℃ Tg.

[045] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-98.9mol%;

Iii) 0.01-is less than the ethylene glycol of 15mol%;

Wherein said polyester has 85-120 ℃ Tg.

[046] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-99mol%,

Wherein the concentration with 0.25g/50ml is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane;

Wherein said polyester has 85-120 ℃ Tg, and randomly, wherein before the polyester or during add one or more branching agents.

[047] on the one hand, the present invention relates to comprise the polymer blend of at least a polyester, described polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

Iii) 0-10mol%'s has an aliphatic dicarboxylic acid residue of 16 carbon atoms at the most;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 1-99mol%; With

(c) from the residue of at least a branching agent;

Wherein the concentration with 0.25g/50ml is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; Wherein

Described polyester has 85-120 ℃ Tg.

[048] on the one hand, the present invention relates to a kind of polymer blend, comprise: at least a polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 1-99mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

Ii) the cyclohexanedimethanol residue of 1-99mol% and

At least a thermo-stabilizer or its reaction product;

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; Wherein said polyester has 85-120 ℃ Tg.

[049] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(I) be selected under at least one temperature of 150 ℃-200 ℃, be selected from a kind of mixture of heating under at least one pressure of 0psig-75psig scope, wherein said mixture comprises:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(ii) 0-30mol%'s has an aromatic dicarboxylic acid residue of 20 carbon atoms at the most; With

(iii) 0-10mol%'s has an aliphatic dicarboxylic acid residue of 16 carbon atoms at the most; With

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

Wherein diol component/the dicarboxylic acid component's who adds in step (I) mol ratio is 1.0-1.5/1.0;

The mixture in the heating steps (I) in the presence of following material wherein:

(i) at least a catalyzer, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide; (ii) at least a thermo-stabilizer, it is selected from least a phosphorus compound, its reaction product and composition thereof;

(II), under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I) product 1-6 hour of heating steps (I), form final polyester at 230 ℃-320 ℃;

Wherein total mol% of the dicarboxylic acid component of final polyester is 100mol%; Wherein total mol% of the diol component of final polyester is 100mol%; Wherein final polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And wherein final polyester has 85-200 ℃ Tg.

[050] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

Wherein diol component/the dicarboxylic acid component's who adds in step (I) mol ratio is 1.05-1.15/1.0;

The mixture in the heating steps (I) in the presence of following material wherein: (i) at least a catalyzer, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide; (ii) at least a thermo-stabilizer, it is selected from least a phosphorus compound, its reaction product and composition thereof;

(II), under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I) product 1-6 hour of heating steps (I), form final polyester at 230 ℃-320 ℃; Wherein total mol% of the dicarboxylic acid component of final polyester is 100mol%; Wherein total mol% of the diol component of final polyester is 100mol%; Wherein final polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And wherein final polyester has 85-200 ℃ Tg.

[051] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of following material wherein: (i) at least a catalyzer, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide;

(II) at 230 ℃-320 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a thermo-stabilizer that is selected from least a phosphorus compound, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour;

[052] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of at least a catalyzer wherein, described catalyzer comprise at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and/or contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide;

[053] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

(II), under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I) product 1-6 hour of heating steps (I), form final polyester at 250 ℃-305 ℃;

[054] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[055] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of at least a catalyzer wherein, described catalyzer comprise at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide;

(II) at 250 ℃-305 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a thermo-stabilizer that is selected from least a phosphorus compound, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour;

[056] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[057] on the one hand, the present invention includes a kind of method that is used to prepare any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of following material wherein: (i) at least a catalyzer, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide; (ii) at least a thermo-stabilizer, it is selected from least a of alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof;

[058] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of following material wherein: (i) at least a catalyzer, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide; (ii) at least a thermo-stabilizer, it is selected from least a of alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof; Form polyester; With

[059] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

(II) at 230 ℃-320 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a at least a thermo-stabilizer that is selected from alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour; Form polyester; With

[060] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

(II) at 230 ℃-320 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a at least a thermo-stabilizer that is selected from alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour; Form polyester;

[061] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[062] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

The mixture in the heating steps (I) in the presence of following material wherein: (i) at least a catalyzer, it comprises at least a tin compound and optional at least a titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contains lithium hydroxide or the aluminum compound of sodium hydroxide; (ii) at least a thermo-stabilizer, it is selected from least a of alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof;

[063] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

(II) at 230 ℃-320 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a at least a thermo-stabilizer that is selected from alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour;

[064] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[065] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[066] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[067] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

(II) at 250 ℃-305 ℃, under at least one pressure of resulting pressure to the 0.02 holder absolute pressure scope that is selected from step (I), in the presence of at least a at least a thermo-stabilizer that is selected from alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof, the product 1-6 of heating steps (I) hour;

[068] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[069] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[070] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[071] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[072] on the one hand, the present invention includes a kind of method that can be used for any polyester of the present invention that is used to prepare, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

[073] on the one hand, polymer blend of the present invention comprises at least a polycarbonate.

[074] on the one hand, polymer blend of the present invention does not comprise polycarbonate.

[075] on the one hand, can be used for polyester of the present invention and comprise the glycol residue that is less than 15mol%, for example 0.01-is less than the glycol residue of 15mol%.

[076] on the one hand, can be used for polyester of the present invention and do not comprise glycol residue.

[077] on the one hand, can be used for the glycol residue that polyester of the present invention comprises 50-99.99mol%.

[078] on the one hand, can be used for polyester of the present invention and do not comprise branching agent, perhaps selectively, before the polyester or during add at least a branching agent.

[079] on the one hand, can be used for polyester of the present invention and comprise at least a branching agent, and the method or the order of not considering to add it.

[080] on the one hand, can be used for polyester of the present invention can't help alone or in combination 1, ammediol or 1,4-butyleneglycol preparation.In others, alone or in combination 1, ammediol or 1,4-butyleneglycol can be used for preparation and can be used for polyester of the present invention.

[081] in one aspect of the invention, the cis-2,2 that can be used for used some polyester of the present invention, 4,4-tetramethyl--1, the mol% of 3-cyclobutanediol is greater than cis-2,2,4,4-tetramethyl--1, the 50mol% of 3-cyclobutanediol or greater than 55mol% or greater than cis-2,2,4,4-tetramethyl--1, the 70mol% of 3-cyclobutanediol; Cis-2,2,4 wherein, 4-tetramethyl--1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl--1, total mol% of 3-cyclobutanediol amounts to and equals 100mol%.

[082] in one aspect of the invention, can be used for 2,2,4 of used some polyester of the present invention, 4-tetramethyl--1, the mol% of the isomer of 3-cyclobutanediol are the cis-2,2 of 30-70mol%, 4,4-tetramethyl--1, trans-2,2 of 3-cyclobutanediol or 30-70mol%, 4,4-tetramethyl--1,3-cyclobutanediol, or the cis of 40-60mol%-2,2,4,4-tetramethyl--1, trans-2,2 of 3-cyclobutanediol or 40-60mol%, 4,4-tetramethyl--1,3-cyclobutanediol, cis-2,2 wherein, 4,4-tetramethyl--1,3-cyclobutanediol and trans-2,2,4,4-tetramethyl--1, total mol% of 3-cyclobutanediol amounts to and equals 100mol%.

[083] on the one hand, it can be amorphous or hemicrystalline can be used for some polyester of the present invention.On the one hand, can be used for some polyester of the present invention and can have lower degree of crystallinity.Therefore can be used for some polyester of the present invention can have essentially amorphous form, means that polyester comprises unordered substantially polymer areas.

[084] on the one hand, can be used for polyester of the present invention and can comprise at least a phosphorus compound, no matter whether exist with thermo-stabilizer.

[085] on the one hand, can be used for polyester of the present invention and can comprise at least a thermo-stabilizer, this thermo-stabilizer comprises at least a phosphorus compound.

[086] on the one hand, can be used for polyester of the present invention and/or polymer blend and can comprise phosphorus atom.

[087] on the one hand, can be used for polyester of the present invention and/or polymer blend and can comprise tin atom.

[088] in one embodiment, can be used for polyester of the present invention and can comprise phosphorus atom and tin atom.

[089] on the one hand, can be used for phosphorus compound of the present invention and comprise phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, phosphonous acid and various ester and salt.Ester can be alkyl, branched-alkyl, substituted alkyl, two sense alkyl, alkyl oxide, aryl and substituted aryl ester.

[090] on the one hand, can be used for phosphorus compound of the present invention and comprise at least a thermo-stabilizer, its reaction product and composition thereof, it is selected from least a of replacement or unsubstituted alkyl phosphate, replacement or unsubstituted aryl phosphate, replacement or unsubstituted mixed phosphate alkyl aryl ester, diphosphites, phosphoric acid salt, phosphine oxide and blended aryl phosphite alkyl ester.Phosphoric acid ester comprises that wherein phosphoric acid is by esterification or the only esterified ester of part fully.

[091] on the one hand, can be used for phosphorus compound of the present invention and comprise at least a thermo-stabilizer, its reaction product and composition thereof, it is selected from least a of replacement or unsubstituted alkyl phosphate, replacement or unsubstituted aryl phosphate, blended replacement or unsubstituted alkyl aryl phosphate.Phosphoric acid ester comprises that wherein phosphoric acid is by esterification or the only esterified ester of part fully.

[092] on the one hand, can be used for phosphorus compound of the present invention and be selected from least a of alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof.

[093] on the one hand, any polymer blend of the present invention can comprise at least a aryl phosphate.

[094] on the one hand, any polymer blend of the present invention can comprise at least a unsubstituted aryl phosphate.

[095] on the one hand, any polymer blend of the present invention can comprise at least a aryl phosphate that is not replaced by benzyl.

[096] on the one hand, any polymer blend of the present invention can comprise at least a triaryl phosphate.

[097] on the one hand, any polymer blend of the present invention can comprise at least a triaryl phosphate that is not replaced by benzyl.

[098] on the one hand, any polymer blend of the present invention can comprise at least a alkyl phosphate.

[099] on the one hand, any polymer blend of the present invention can comprise Triphenyl phosphate and/or Merpol A.In one embodiment, any polymer blend of the present invention can comprise Triphenyl phosphate.

[0100] on the one hand, can be used for phosphorus compound of the present invention can be selected from following at least a: diphosphites, phosphoric acid salt, phosphine oxide and blended aryl phosphite alkyl ester.

[0101] in one embodiment, can be used for phosphorus compound of the present invention and include but not limited at least a diphosphites.

[0102] in one embodiment, can be used for phosphorus compound of the present invention and include but not limited at least a diphosphites, it comprises 2,4,8,10-four oxa-s-3,9-two phospha spiral shell [5.5] undecane structures, for example Weston 619 (GE Specialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0103] on the one hand, can be used for phosphorus compound of the present invention and comprise at least a blended phosphorous acid alkyl aryl ester, for example two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, be also referred to as Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0104] in one embodiment, can be used for phosphorus compound of the present invention and be included at least a phosphine oxide.

[0105] in one embodiment, can be used for phosphorus compound of the present invention and comprise at least a phosphoric acid salt, for example KH ₂PO ₄And Zn ₃(PO ₄) ₂

[0106] on the one hand, any method that is used to prepare polymer blend and/or polyester as herein described comprises at least a phosphorus compound as herein described.

[0107] on the one hand, any method that is used to prepare polymer blend and/or polyester as herein described can comprise at least a diphosphites.On the one hand, the any method that is used to prepare polymer blend and/or polyester as herein described can comprise at least a diphosphites, it comprises 2,4,8,10-four oxa-s-3,9-two phospha spiral shell [5.5] undecane structures, for example Weston 619 (GESpecialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (DoverChemicals, CAS#154862-43-8).

[0108] it is believed that any method that preparation can be used for polyester of the present invention can be used for preparation and can be used for any polyester of the present invention.

[0109] on the one hand, used pressure comprises at least one pressure that is selected from 0psig-75psig in the step (I) of any method of the present invention.In one embodiment, used pressure comprises at least one pressure that is selected from 0psig-50psig in the step (I) of any method of the present invention.

[0110] on the one hand, used pressure comprises at least one pressure that is selected from 20 holder absolute pressure-0.02 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 10 holder absolute pressure-0.02 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 5 holder absolute pressure-0.02 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 3 holder absolute pressure-0.02 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 20 holder absolute pressure-0.1 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 10 holder absolute pressure-0.1 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 5 holder absolute pressure-0.1 holder absolute pressures in the step (II) of any method of the present invention; In one embodiment, used pressure comprises at least one pressure that is selected from 3 holder absolute pressure-0.1 holder absolute pressures in the step (II) of any method of the present invention.

[0111] on the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.0-1.5/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.5/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.3/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.2/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.15/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.10/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.5/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.3/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.2/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.15/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.10/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.5/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.3/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.2/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.15/1.0; On the one hand, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.10/1.0.

[0112] be used for preparing any method embodiment that can be used for polyester of the present invention, can be 1-5 hour the heat-up time of step (II).Be used for preparing any method embodiment that can be used for polyester of the present invention, can be 1-4 hour the heat-up time of step (II).Be used for preparing any method embodiment that can be used for polyester of the present invention, can be 1-3 hour the heat-up time of step (II).Be used for preparing any method embodiment that can be used for polyester of the present invention, can be 1.5-3 hour the heat-up time of step (II).Be used for preparing any method embodiment that can be used for polyester of the present invention, can be 1-2 hour the heat-up time of step (II).

[0113] on the one hand, any polymer blend of the present invention and/or method can comprise at least a tin compound as described herein.

[0114] on the one hand, any polymer blend of the present invention and/or method can comprise at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminum compound and contain lithium hydroxide or the catalyzer of the aluminum compound of sodium hydroxide.

[0115] in one embodiment, the method that can be used for any polymer blend of the present invention and/or prepare polyester can be used and be selected from least a tin compound and at least a titanium compound prepares as catalyzer.

[0116] in one embodiment, adding the weight ratio that phosphorus compound can obtain in the final polyester total tin atom and total phosphorus atom in the methods of the invention is 2-10: 1.In one embodiment, in described method, add phosphorus compound and can obtain that the weight ratio of total tin atom and total phosphorus atom is 5-9 in the final polyester: 1.In one embodiment, in described method, add phosphorus compound and can obtain that the weight ratio of total tin atom and total phosphorus atom is 6-8 in the final polyester: 1.In one embodiment, in described method, add phosphorus compound and can obtain that the weight ratio of total tin atom and total phosphorus atom is 7: 1 in the final polyester.

[0117] in one embodiment, the amount of tin atom can be the 15-400ppm tin atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0118] in one embodiment, the amount of tin atom can be the 25-400ppm tin atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0119] in one embodiment, the amount of tin atom can be the 40-200ppm tin atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0120] in one embodiment, the amount of tin atom can be the 50-125ppm tin atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0121] in one embodiment, the amount of phosphorus atom can be the 1-100ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0122] in one embodiment, the amount of phosphorus atom can be the 4-60ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0123] in one embodiment, the amount of phosphorus atom can be the 6-20ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester.

[0124] in one embodiment, the amount of phosphorus atom can be the 1-100ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester, and the amount of tin atom can be the 15-400ppm tin atom in final polyester, based on the weight of final polyester.

[0125] in one embodiment, the amount of phosphorus atom can be the 1-100ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester, and the amount of tin atom can be the 25-400ppm tin atom in final polyester, based on the weight of final polyester.

[0126] in one embodiment, the amount of phosphorus atom can be the 4-60ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester, and the amount of tin atom can be the 40-200ppm tin atom in final polyester, based on the weight of final polyester.

[0127] in one embodiment, the amount of phosphorus atom can be the 6-20ppm phosphorus atom in can be used for final polyester of the present invention, based on the weight of final polyester, and the amount of tin atom can be the 50-125ppm tin atom in final polyester, based on the weight of final polyester.

[0128] on the one hand, the any method that is used to prepare any polymer blend and/or polyester as herein described can comprise at least a blended phosphorous acid alkyl aryl ester, for example two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, be also referred to as Doverphos S-9228 (DoverChemicals, CAS#154862-43-8).

[0129] on the one hand, any method that is used to prepare any polymer blend and/or polyester as herein described can comprise at least a phosphine oxide.

[0130] on the one hand, any method that is used to prepare any polymer blend and/or polyester as herein described can comprise at least a phosphoric acid salt, for example KH ₂PO ₄And Zn ₃(PO ₄) ₂

[0131] on the one hand, polymer blend can be used for making goods, include but not limited to extrusion molding, calendering and/or moulded parts, include but not limited to injection-molded item, extrudate, curtain coating extrudate, profile extrusion goods, melt-spun goods, thermoformed articles, extrusion molding moulded product, injection blow molding moulded product, injection stretch blow moulded product, extrusion blow molded moulded product and crowded base stretch-blow moulded product.These goods can include but not limited to film, bottle container, thin plate and/or fiber.

[0132] on the one hand, can be used for polymer blend of the present invention and can be used for various types of films and/or thin plate, include but not limited to cast film and/or thin plate, calendered film and/or thin plate, compression molded films and/or thin plate, solution casting film and/or thin plate.The method for preparing film and/or thin plate includes but not limited to extrusion molding, calendering, compression moulding and solution casting.

[0133] same, on the one hand, use these special polymer blends before melt-processed and/or thermoforming, to minimize and/or get rid of drying step.

The accompanying drawing summary

[0134] Fig. 1 shows the figure of comonomer to the influence of the fastest hypocrystalline time of modification PCT copolyesters.

[0135] Fig. 2 is presented at the middle comonomer of notched izod impact strength test (ASTM D256,1/8 inch thick, 10 mil breach) to brittle-ductile transition temperature (T _Bd) the figure of influence.

[0136] Fig. 3 shows 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is formed the figure to the influence of the second-order transition temperature (Tg) of copolyesters.

Detailed Description Of The Invention

[0137] by can more easily understanding the present invention with reference to the detailed description of following certain embodiments of the invention and work embodiment. According to purpose of the present invention, certain embodiments of the present invention are recorded in the summary of the invention and are further described under this. Equally, other embodiment of the present invention is described in this.

[0138] it is believed that and as herein describedly can be used for polyester of the present invention and can have such as high impact, medium glass transition temperature (Tg or T_g), the combination of two or more physical properties of chemical resistance, hydrolytic stability, toughness, low ductile-brittle transition temperature, good color and transparency, low-density, long flexible chain and good processability, allow easily thus them to be configured as goods. In some embodiments of the present invention, polyester has special performance combination and/or the performance combination of good impact strength, heat resistance and processability and/or the combination of two or more above-mentioned performances of good impact strength, heat resistance, chemical resistance, density, never thinks in the past that these performances combinations were present in the polyester.

[0139] used term " polyester " is intended comprising copolyesters and is interpreted as representing reacting the synthetic polymer for preparing by one or more bifunctional carboxylic acids and/or polyfunctional carboxylic acids with one or more difunctionality hydroxy compounds and/or multifunctional hydroxy compounds herein. Usually the bifunctional carboxylic acid can be dicarboxylic acids, and the difunctionality hydroxy compounds can be dihydroxy alcohol, for example dihydroxylic alcohols and glycol. Used term " glycol " includes but not limited to glycol, dihydroxylic alcohols and/or multifunctional hydroxy compounds, for example branching agent among the application. Selectively, the bifunctional carboxylic acid can be hydroxycarboxylic acid, P-hydroxybenzoic acid for example, and the difunctionality hydroxy compounds can be the virtue nuclear with 2 hydroxyl substituents, for example quinhydrones. Used term " residue " expression herein is incorporated into any organic structure in the polymer by polycondensation and/or esterification by corresponding monomer. Used term " repetitive " expression herein has dicarboxylic acid residue and the diol residue by the combination of carbonyl oxygen base. Therefore, for example, dicarboxylic acid residue can be derived from carboxylic acid halides, ester, salt, acid anhydrides or its mixture of dicarboxylic acid monomer or its combination. Therefore, used term dicarboxylic acids intends comprising any derivative of dicarboxylic acids and dicarboxylic acids herein, comprises the carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture that can be used for reacting with glycol its combination of the course of reaction for preparing polyester. In addition, the used term of the application " diacid " comprises polyfunctional acid, for example branching agent. Any derivative of terephthalic acid (TPA) itself and residue and terephthalic acid (TPA) intended comprising in used term " terephthalic acid (TPA) " herein, comprises carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed acid anhydride or its mixture or its residue that can be used for reacting with glycol its combination of the course of reaction for preparing polyester.

[0140] in one embodiment, terephthalic acid (TPA) can be used as raw material. In another embodiment, dimethyl terephthalate (DMT) can be used as raw material. In another embodiment, the mixture of terephthalic acid (TPA) and dimethyl terephthalate (DMT) can be used as raw material and/or intermediate materials.

[0141] is used for polyester of the present invention and usually can and be incorporated into polyester polymers as dicarboxylic acids and the glycol preparation of their corresponding residue by equal proportion reaction basically. Therefore, polyester of the present invention can comprise basically sour residue (100mol%) and glycol (and/or multifunctional hydroxy compounds) residue (100mol%) of equimolar ratio, so that the total mole number of repetitive equals 100 mol%. Therefore, the molar percentage that provides in the present disclosure can be based on the total mole number of sour residue, the total mole number of diol residue or the total mole number of repetitive. For example, based on the total acid residue, polyester comprises the 30mol% M-phthalic acid, is illustrated in altogether that polyester comprises the 30mol% isophthalic acid residues in the 100mol% acid residue. Therefore, in every 100mol acid residue, there is the 30mol isophthalic acid residues. In another example, based on the total diol residue, polyester comprises the 30mol% TMCBD, is illustrated in altogether that polyester comprises 30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol residue in the 100mol% diol residue. Therefore, in every 100mol diol residue, there is 30mol TMCBD residue.

[0142] in other side of the present invention, the Tg that can be used for polyester of the present invention can be at least one of following scope: 85-130 ℃; 85-125 ℃; 85-120 ℃; 85-115 ℃; 85-110 ℃; 85-105 ℃; 85-100 ℃; 85-95 ℃; 85-90 ℃; 90-130 ℃; 125 ℃ of 90-; 90-120 ℃; 90-115 ℃; 90-110 ℃; 90-105 ℃; 90-100 ℃; 95 ℃ of 90-; 95-130 ℃; 95-125 ℃; 95-120 ℃; 95-115 ℃; 95-110 ℃; 105 ℃ of 95-; 95-100 ℃; 100-130 ℃; 100-125 ℃; 100-120 ℃; 100-115 ℃; 100-110 ℃; 100-105 ℃; 105-130 ℃; 105-125 ℃; 105-120 ℃; 115 ℃ of 105-; 105-110 ℃; Be higher than 105-130 ℃; Be higher than 105-125 ℃; Be higher than 120 ℃ of 105-; Be higher than 105-115 ℃; Be higher than 105-110 ℃; 110-130 ℃; 110-125 ℃; 110-120 ℃; 110-115 ℃; 115-130 ℃; 115-125 ℃; 115-120 ℃; 130 ℃ of 115-; 115-125 ℃; 115-120 ℃; 120-130 ℃; With 125-130 ℃.

[0143] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 1-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-99mol% cyclohexanedimethanol; 1-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-99mol% cyclohexanedimethanol; 1-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-99mol% cyclohexanedimethanol; 1-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-99mol% cyclohexanedimethanol; 1-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-99mol% cyclohexanedimethanol; 1-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-99mol% cyclohexanedimethanol; 1-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-99mol% cyclohexanedimethanol; 1-65mol% TMCBD and 35-99mol% cyclohexanedimethanol; 1-60 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-99mol% cyclohexanedimethanol; 1-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-99mol% cyclohexanedimethanol; 1-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-99mol% cyclohexanedimethanol; 1-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-99mol% cyclohexanedimethanol; 1-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-99mol% cyclohexanedimethanol; 1-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-99mol% cyclohexanedimethanol; 1-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-99mol% cyclohexanedimethanol; 1-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-99mol% cyclohexanedimethanol; 1-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-99mol% cyclohexanedimethanol; 1-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-99mol% cyclohexanedimethanol; 1-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-99mol% cyclohexanedimethanol; And 1-5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95-99 mol% cyclohexanedimethanol; Greater than 0.01-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90-are less than the 99.99mol% cyclohexanedimethanol; And greater than 0.01-5mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95-are less than the 99.99mol% cyclohexanedimethanol.

[0144] in other side of the present invention, the diol component that can be used for the polyester of film of the present invention or thin plate includes but not limited at least a in the following combination range: 5-99mol% 2,2, and 4,4-tetramethyl-1,3-cyclobutanediol and 1-95mol% cyclohexanedimethanol; 5-95mol% TMCBD and 5-95mol% cyclohexanedimethanol; 5-90mol% TMCBD and 10 1 95mol% cyclohexanedimethanols; 5-85 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-95mol% cyclohexanedimethanol; 5-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-95mol% cyclohexanedimethanol; 5-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-95mol% cyclohexanedimethanol; 5-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-95mol% cyclohexanedimethanol; 5-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-95mol% cyclohexanedimethanol; 5-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-95mol% cyclohexanedimethanol; 5-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-95mol% cyclohexanedimethanol; And 5-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-95mol% cyclohexanedimethanol.

[0145] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 5-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 50-95mol% cyclohexanedimethanol; 5-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-95mol% cyclohexanedimethanol; 5-40mol% TMCBD and 60-95mol% cyclohexanedimethanol; 5-35 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-95mol% cyclohexanedimethanol; 5-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 65-95mol% cyclohexanedimethanol; 5-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-95mol% cyclohexanedimethanol; 5-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-95mol% cyclohexanedimethanol; 5-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-95mol% cyclohexanedimethanol; 5-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-95mol% cyclohexanedimethanol; And 5-10mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-90 mol% cyclohexanedimethanol.

[0146] in other side of the present invention, the diol component that can be used for the polyester of film of the present invention or thin plate includes but not limited at least a in the following combination range: 10-99mol% 2,2, and 4,4-tetramethyl-1,3-cyclobutanediol and 1-90mol% cyclohexanedimethanol; 10-95 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-90mol% cyclohexanedimethanol; 10-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-90mol% cyclohexanedimethanol; 10-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-90mol% cyclohexanedimethanol; 10-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-90mol% cyclohexanedimethanol; 10-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-90mol% cyclohexanedimethanol; 10-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-90mol% cyclohexanedimethanol; 10-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-90mol% cyclohexanedimethanol; 10-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-90mol% cyclohexanedimethanol; 10-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-90mol% cyclohexanedimethanol; And 10-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-90mol% cyclohexanedimethanol.

[0147] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 10-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 50-90mol% cyclohexanedimethanol; 10-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-90mol% cyclohexanedimethanol; 10-40mol% TMCBD and 60-90mol% cyclohexanedimethanol; 10-35 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-90mol% cyclohexanedimethanol; 10-is less than 35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 65-90mol% cyclohexanedimethanol; 10-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-90mol% cyclohexanedimethanol; 10-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-90mol% cyclohexanedimethanol; 10-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-90mol% cyclohexanedimethanol; And 10-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 85-90mol% cyclohexanedimethanol.

[0148] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 11-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-89mol% cyclohexanedimethanol; 11-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-89mol% cyclohexanedimethanol; 11-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-89mol% cyclohexanedimethanol; 11-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-89mol% cyclohexanedimethanol; 11-80mol% TMCBD and 20-89mol% cyclohexanedimethanol; 11-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-89mol% cyclohexanedimethanol; 11-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-89mol% cyclohexanedimethanol; 11-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-89mol% cyclohexanedimethanol; 11-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-89mol% cyclohexanedimethanol; 11-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-89mol% cyclohexanedimethanol; And 11-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-89mol% cyclohexanedimethanol.

[0149] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 11-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the maximum 89mol% cyclohexanedimethanols of 50-; 11-45mol% TMCBD and 55-89mol% cyclohexanedimethanol; 11-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-89mol% cyclohexanedimethanol; 11-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-89mol% cyclohexanedimethanol; 11-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-89mol% cyclohexanedimethanol; 11-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-89mol% cyclohexanedimethanol; 11-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-89mol% cyclohexanedimethanol; And 11-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-85mol% cyclohexanedimethanol.

[0150] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 12-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-86mol% cyclohexanedimethanol; 12-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-88mol% cyclohexanedimethanol; 12-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-88mol% cyclohexanedimethanol; 12-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-88mol% cyclohexanedimethanol; 12-86mol% TMCBD and 14-88mol% cyclohexanedimethanol; 12-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-88mol% cyclohexanedimethanol; 12-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-88mol% cyclohexanedimethanol; 12-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-88mol% cyclohexanedimethanol; 12-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-88mol% cyclohexanedimethanol; 12-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-88mol% cyclohexanedimethanol; And 12-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-88mol% cyclohexanedimethanol.

[0151] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 12-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the maximum 88mol% cyclohexanedimethanols of 50-; 12-45mol% TMCBD and 55-88mol% cyclohexanedimethanol; 12-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-88mol% cyclohexanedimethanol; 12-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-88mol% cyclohexanedimethanol; 12-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-88mol% cyclohexanedimethanol; 12-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-88mol% cyclohexanedimethanol; 12-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-88mol% cyclohexanedimethanol; And 12-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-88mol% cyclohexanedimethanol.

[0152] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 13-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-87mol% cyclohexanedimethanol; 13-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-87mol% cyclohexanedimethanol; 13-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-87mol% cyclohexanedimethanol; 13-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-87mol% cyclohexanedimethanol; 13-80mol% TMCBD and 20-87mol% cyclohexanedimethanol; 13-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-87mol% cyclohexanedimethanol; 13-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-87mol% cyclohexanedimethanol; 13-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-87mol% cyclohexanedimethanol; 13-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-87mol% cyclohexanedimethanol; 13-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-87mol% cyclohexanedimethanol; And 13-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-87mol% cyclohexanedimethanol.

[0153] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 13-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the maximum 87mol% cyclohexanedimethanols of 50-; 13-45mol% TMCBD and 55-87mol% cyclohexanedimethanol; 13-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-87mol% cyclohexanedimethanol; 13-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-87mol% cyclohexanedimethanol; 13-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-87mol% cyclohexanedimethanol; 13-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-87mol% cyclohexanedimethanol; 13-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-87mol% cyclohexanedimethanol; And 13-15mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85-87mol% cyclohexanedimethanol.

[0154] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 14-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-86mol% cyclohexanedimethanol; 14-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-86mol% cyclohexanedimethanol; 14-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-86mol% cyclohexanedimethanol; 14-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-86mol% cyclohexanedimethanol; 14-86mol% TMCBD and 14-86mol% cyclohexanedimethanol; 14-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-86mol% cyclohexanedimethanol; 14-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-86mol% cyclohexanedimethanol; 14-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-86mol% cyclohexanedimethanol; 14-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-86mol% cyclohexanedimethanol; 14-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-86mol% cyclohexanedimethanol; And 14-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-86mol% cyclohexanedimethanol.

[0155] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 14-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the maximum 86mol% cyclohexanedimethanols of 50-; 14-45mol% TMCBD and 55-86mol% cyclohexanedimethanol; 14-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-86mol% cyclohexanedimethanol; 14-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-86mol% cyclohexanedimethanol; 14-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-86mol% cyclohexanedimethanol; 14-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-86mol% cyclohexanedimethanol; And 14-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-86mol% cyclohexanedimethanol.

[0156] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 15-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-85mol% cyclohexanedimethanol; 15-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-85mol% cyclohexanedimethanol; 15-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-85mol% cyclohexanedimethanol; 15-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-85mol% cyclohexanedimethanol; 15-85mol% TMCBD and 15-85mol% cyclohexanedimethanol; 15-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-85mol% cyclohexanedimethanol; 15-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-85mol% cyclohexanedimethanol; 15-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-85mol% cyclohexanedimethanol; 15-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-85mol% cyclohexanedimethanol; 15-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-85mol% cyclohexanedimethanol; And 15-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-85mol% cyclohexanedimethanol.

[0157] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 15-less than 50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the maximum 85mol% cyclohexanedimethanols of 50-; 15-45mol% TMCBD and 55-85mol% cyclohexanedimethanol; 15-40 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-85mol% cyclohexanedimethanol; 15-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-85mol% cyclohexanedimethanol; 15-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-85mol% cyclohexanedimethanol; 15-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-85mol% cyclohexanedimethanol; 15-20mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80-85mol% cyclohexanedimethanol; And 17-23mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77-83mol% cyclohexanedimethanol;

[0158] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 20-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-80mol% cyclohexanedimethanol; 20-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-80mol% cyclohexanedimethanol; 20-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-80mol% cyclohexanedimethanol; 20-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-80mol% cyclohexanedimethanol; 20-80mol% TMCBD and 20-80mol% cyclohexanedimethanol; 20-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-80mol% cyclohexanedimethanol; 20-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-80mol% cyclohexanedimethanol; 20-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-80mol% cyclohexanedimethanol; 20-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-80mol% cyclohexanedimethanol; 20-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-80mol% cyclohexanedimethanol; 20-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-80mol% cyclohexanedimethanol; 20-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-80mol% cyclohexanedimethanol; 20-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-80mol% cyclohexanedimethanol; 20-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-80mol% cyclohexanedimethanol; 20-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-80 mol% cyclohexanedimethanol; And 20-25mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75-80mol% cyclohexanedimethanol.

[0159] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 25-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-75mol% cyclohexanedimethanol; 25-95mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5-75mol% cyclohexanedimethanol; 25-90mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10-75mol% cyclohexanedimethanol; 25-85mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15-75mol% cyclohexanedimethanol; 25-80mol% TMCBD and 20-75mol% cyclohexanedimethanol; 25-75 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-75mol% cyclohexanedimethanol; 25-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-75mol% cyclohexanedimethanol; 25-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-75mol% cyclohexanedimethanol; 25-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-75mol% cyclohexanedimethanol; 25-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-75mol% cyclohexanedimethanol; 25-50mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50-75mol% cyclohexanedimethanol; 25-45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55-75mol% cyclohexanedimethanol; 25-40mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60-75mol% cyclohexanedimethanol; 25-35mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65-75mol% cyclohexanedimethanol; 25-30mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70-75 mol% cyclohexanedimethanol.

[0160] in other side of the present invention, the diol component that can be used for polyester of the present invention includes but not limited at least a in the following combination range: 35-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-65mol% cyclohexanedimethanol; 37-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-63mol% cyclohexanedimethanol; 40-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-60mol% cyclohexanedimethanol; 45-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-55mol% cyclohexanedimethanol; 50-80mol% TMCBD and 20-50mol% cyclohexanedimethanol; Greater than 50-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-are less than the 50mol% cyclohexanedimethanol; 55-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-45mol% cyclohexanedimethanol; 60-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-40mol% cyclohexanedimethanol; 65-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-35mol% cyclohexanedimethanol; 70-80mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-30mol% cyclohexanedimethanol; 40-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-60mol% cyclohexanedimethanol; 45-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-55 mol% cyclohexanedimethanol; 50-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-50mol% cyclohexanedimethanol; 55-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-45mol% cyclohexanedimethanol; 60-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-40mol% cyclohexanedimethanol; 65-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-35mol% cyclohexanedimethanol; 40-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-60mol% cyclohexanedimethanol; 45-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-55mol% cyclohexanedimethanol; 50-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-50mol% cyclohexanedimethanol; Greater than 50-99mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1-are less than the 50mol% cyclohexanedimethanol; Greater than 50-80 mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20-are less than the 50mol% cyclohexanedimethanol; Greater than 50-75mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25-are less than the 50mol% cyclohexanedimethanol; Greater than 50-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-are less than the 50mol% cyclohexanedimethanol; 55-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-45mol% cyclohexanedimethanol; 60-70mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30-40mol% cyclohexanedimethanol; 40-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-60mol% cyclohexanedimethanol; 40-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-60mol% cyclohexanedimethanol; 40-is less than 45mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than the 55-60mol% cyclohexanedimethanol; 45-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-55mol% cyclohexanedimethanol; Greater than 50-65mol% TMCBD and 35-less than the 50mol% cyclohexanedimethanol; 50-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-50mol% cyclohexanedimethanol; 55-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-45mol% cyclohexanedimethanol; 40-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-60mol% cyclohexanedimethanol; 45-60mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40-55mol% cyclohexanedimethanol; 45-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-55mol% cyclohexanedimethanol; Greater than 45-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-are less than 55 mol% cyclohexanedimethanols; And 46-55mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45-54mol% cyclohexanedimethanol; And 46-65mol%2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35-54mol% cyclohexanedimethanol.

[0161] except above-mentioned listed glycol, the polyester that can be used for polymer blend of the present invention also can be by 1,3-PD, BDO or the preparation of its mixture.

[0162] except above-mentioned listed glycol, the polyester that can be used for polymer blend of the present invention also can be by 1, ammediol, 1,4-butanediol or the preparation of its mixture, it can have at least one of at least one of Tg scope described herein, logarithmic viscosity number scope described herein and/or at least one of glycol described herein or two acid ranges. In addition or selectively, can also can be by 1,4-CHDM with at least a following amount preparation: 0.1-99mol% by the polyester of 1,3-PD or BDO or the preparation of its mixture; 0.1-95mol%; 0.1-90mol%; 0.1-85mol%; 0.1-80mol%; 0.1-70mol%; 0.1-60mol%; 0.1-50mol%; 0.1-40mol%; 0.1-35mol%; 0.1-30mol%; 0.1-25mol%; 0.1-20mol%; 0.1-15 mol%; 0.1-10mol%; 0.1-5mol%; 1-99mol%; 1-95mol%; 1-90 mol%; 1-85mol%; 1-80mol%; 1-70mol%; 1-60mol%; 1-50mol%; 1-40mol%; 1-35mol%; 1-30mol%; 1-25mol%; 1-20mol%; 1-15mol%; 1-10mol%; 1-5mol%; 5-99mol%; 5-95mol%; 5-90 mol%; 5-85mol%; 5-80mol%; 5-70mol%; 5-60mol%; 5-50mol%; 5-40mol%; 5-35mol%; 5-30mol%; 5-25mol%; 5-20mol%; With 5-15mol%; 5-10mol%; 10-99mol%; 10-95mol%; 10-90mol%; 10-85mol%; 10-80mol%; 10-70mol%; 10-60mol%; 10-50mol%; 10-40mol%; 10-35mol%; 10-30mol%; 10-25mol%; 10-20mol%; 10-15mol%; 20-99mol%; 20-95mol%; 20-90mol%; 20-85mol%; 20-80mol%; 20-70mol%; 20-60mol%; 20-50mol%; 20-40mol%; 20-35mol%; 20-30mol%; And 20-25mol%.

[0163] for certain embodiments of the present invention, can be used for polyester of the present invention and can be presented in 60/40 (wt/wt) phenol/tetrachloroethanes with the concentration of 0.25g/50ml at least one following logarithmic viscosity number: 0.10-1.2dL/g 25 ℃ of mensuration; 0.10-1.1dL/g; 0.10-1dL/g; 0.10-less than 1dL/g; 0.10-0.98dL/g; 0.10-0.95dL/g; 0.10-0.90dL/g; 0.10-0.85dL/g; 0.10-0.80dL/g; 0.10-0.75dL/g; 0.10-less than 0.75dL/g; 0.10-0.72dL/g; 0.10-0.70dL/g; 0.10-less than 0.70dL/g; 0.10-0.68dL/g; 0.10-less than 0.68dL/g; 0.10-0.65dL/g; 0.20-1.2dL/g; 0.20-1.1dL/g; 0.20-1dL/g; 0.20-less than 1dL/g; 0.20-0.98dL/g; 0.20-0.95dL/g; 0.20-0.90dL/g; 0.20-0.85dL/g; 0.20-0.80dL/g; 0.20-0.75dL/g; 0.20-less than 0.75dL/g; 0.20-0.72dL/g; 0.20-0.70dL/g; 0.20-less than 0.70dL/g; 0.20-0.68dL/g; 0.20-less than 0.68dL/g; 0.20-0.65dL/g; 0.35-1.2dL/g; 0.35-1.1dL/g; 0.35-1dL/g; 0.35-less than 1dL/g; 0.35-0.98dL/g; 0.35-0.95dL/g; 0.35-0.90dL/g; 0.35-0.85dL/g; 0.35-0.80dL/g; 0.35-0.75 dL/g; 0.35-less than 0.75dL/g; 0.35-0.72dL/g; 0.35-0.70dL/g; 0.35-less than 0.70dL/g; 0.35-0.68dL/g; 0.35-less than 0.68dL/g; 0.35-0.65dL/g; 0.40-1.2dL/g; 0.40-1.1dL/g; 0.40-1dL/g; 0.40-less than 1dL/g; 0.40-0.98 dL/g; 0.40-0.95dL/g; 0.40-0.90dL/g; 0.40-0.85dL/g; 0.40-0.80dL/g; 0.40-0.75dL/g; 0.40-less than 0.75dL/g; 0.40-0.72dL/g; 0.40-0.70dL/g; 0.40-less than 0.70dL/g; 0.40-0.68dL/g; 0.40-less than 0.68dL/g; 0.40-0.65 dL/g; Greater than 0.42-1.2dL/g; Greater than 0.42-1.1dL/g; Greater than 0.42-1dL/g; Greater than 0.42-less than 1dL/g; Greater than 0.42-0.98dL/g; Greater than 0.42-0.95dL/g; Greater than 0.42-0.90dL/g; Greater than 0.42-0.85dL/g; Greater than 0.42-0.80dL/g; Greater than 0.42-0.75dL/g; Greater than 0.42-less than 0.75dL/g; Greater than 0.42-0.72dL/g; Greater than 0.42-less than 0.70dL/g; Greater than 0.42-0.68dL/g; Greater than 0.42-less than 0.68dL/g; With greater than 0.42-0.65dL/g.

[0164] for certain embodiments of the present invention, can be used for polyester of the present invention and can be presented in 60/40 (wt/wt) phenol/tetrachloroethanes with the concentration of 0.25g/50ml at least one following logarithmic viscosity number: 0.45-1.2dL/g 25 ℃ of mensuration; 0.45-1.1dL/g; 0.45-1dL/g; 0.45-0.98dL/g; 0.45-0.95dL/g; 0.45-0.90dL/g; 0.45-0.85dL/g; 0.45-0.80dL/g; 0.45-0.75dL/g; 0.45-less than 0.75dL/g; 0.45-0.72dL/g; 0.45-0.70dL/g; 0.45-less than 0.70dL/g; 0.45-0.68dL/g; 0.45-less than 0.68dL/g; 0.45-0.65dL/g; 0.50-1.2dL/g; 0.50-1.1dL/g; 0.50-1dL/g; 0.50-less than 1dL/g; 0.50-0.98dL/g; 0.50-0.95dL/g; 0.50-0.90dL/g; 0.50-0.85 dL/g; 0.50-0.80dL/g; 0.50-0.75dL/g; 0.50-less than 0.75dL/g; 0.50-0.72 dL/g; 0.50-0.70dL/g; 0.50-less than 0.70dL/g; 0.50-0.68dL/g; 0.50-less than 0.68dL/g; 0.50-0.65dL/g; 0.55-1.2dL/g; 0.55-1.1dL/g; 0.55-1dL/g; 0.55-less than 1dL/g; 0.55-0.98dL/g; 0.55-0.95dL/g; 0.55-0.90dL/g; 0.55-0.85dL/g; 0.55-0.80dL/g; 0.55-0.75dL/g; 0.55-less than 0.75dL/g; 0.55-0.72dL/g; 0.55-0.70dL/g; 0.55-less than 0.70dL/g; 0.55-0.68dL/g; 0.55-less than 0.68dL/g; 0.55-0.65dL/g; 0.58-1.2dL/g; 0.58-1.1dL/g; 0.58-1dL/g; 0.58-less than 1dL/g; 0.58-0.98dL/g; 0.58-0.95dL/g; 0.58-0.90dL/g; 0.58-0.85dL/g; 0.58-0.80dL/g; 0.58-0.75dL/g; 0.58-less than 0.75dL/g; 0.58-0.72dL/g; 0.58-0.70dL/g; 0.58-less than 0.70dL/g; 0.58-0.68dL/g; 0.58-less than 0.68dL/g; 0.58-0.65dL/g; 0.60-1.2dL/g; 0.60-1.1dL/g; 0.60-1dL/g; 0.60-less than 1dL/g; 0.60-0.98dL/g; 0.60-0.95 dL/g; 0.60-0.90dL/g; 0.60-0.85dL/g; 0.60-0.80dL/g; 0.60-0.75dL/g; 0.60-less than 0.75dL/g; 0.60-0.72dL/g; 0.60-0.70dL/g; 0.60-less than 0.70 dL/g; 0.60-0.68dL/g; 0.60-less than 0.68dL/g; 0.60-0.65dL/g; 0.65-1.2 dL/g; 0.65-1.1dL/g; 0.65-1dL/g; 0.65-less than 1dL/g; 0.65-0.98dL/g; 0.65-0.95dL/g; 0.65-0.90dL/g; 0.65-0.85dL/g; 0.65-0.80dL/g; 0.65-0.75dL/g; 0.65-less than 0.75dL/g; 0.65-0.72dL/g; 0.65-0.70dL/g; 0.65-less than 0.70dL/g; 0.68-1.2dL/g; 0.68-1.1dL/g; 0.68-1dL/g; 0.68-less than 1dL/g; 0.68-0.98dL/g; 0.68-0.95dL/g; 0.68-0.90dL/g; 0.68-0.85 dL/g; 0.68-0.80dL/g; 0.68-0.75dL/g; 0.68-less than 0.75dL/g; 0.68-0.72 dL/g; Greater than 0.76dL/g-1.2dL/g; Greater than 0.76dL/g-1.1dL/g; Greater than 0.76dL/g-1dL/g; Greater than 0.76dL/g-less than 1dL/g; Greater than 0.76dL/g-0.98dL/g; Greater than 0.76dL/g-0.95dL/g; Greater than 0.76dL/g-0.90dL/g; Greater than 0.80dL/g-1.2 dL/g; Greater than 0.80dL/g-1.1dL/g; Greater than 0.80dL/g-1dL/g; Greater than 0.80dL/g-less than 1dL/g; Greater than 0.80dL/g-1.2dL/g; Greater than 0.80dL/g-0.98dL/g; Greater than 0.80dL/g-0.95dL/g; Greater than 0.80dL/g-0.90dL/g.

[0165] unless otherwise indicated, expection can be used for polyester of the present invention and can have at least one of logarithmic viscosity number scope as herein described and at least one of the monomer scope for polyester as herein described. Unless otherwise indicated, also expection can be used at least one of monomer scope that polyester of the present invention can have at least one of Tg scope as herein described and be used for polyester as herein described. Unless otherwise indicated, also expection can be used at least one of monomer scope that polyester of the present invention can have at least one of at least one of Tg scope as herein described, logarithmic viscosity number scope as herein described and be used for composition as herein described.

[0166] for required polyester, the mol ratio of cis/trans TMCBD is owing to pure form or its mixture separately can change. In certain embodiments, the molar percentage of cis and/or trans TMCBD is greater than 50mol% cis and trans less than 50mol%; Or greater than 55mol% cis and trans less than 45mol%; Or 30-70mol% cis and 70-30mol% are trans; Or 40-60mol% cis and 60-40 mol% are trans; Or the trans and 50-30mol% cis of 50-70mol% or 50-70mol% cis and 50-30mol% are trans; Or 60-70mol% cis and 30-40mol% are trans; Or greater than 70mol% cis and trans less than 30mol%; Wherein cis-and the summation of the molar percentage of trans-TMCBD equal 100mol%. The mol ratio of cis/trans 1,4-CHDM can at 50/50-0/100, for example change in the scope of 40/60-20/80.

[0167] in certain embodiments, terephthalic acid (TPA) or its ester, the mixture of dimethyl terephthalate (DMT) or terephthalic acid (TPA) and ester thereof for example is configured for forming the most of of the dicarboxylic acid component that can be used for polyester of the present invention or all. In certain embodiments, the terephthalic acid residue can be with 70mol% at least, as 80mol% at least, at least 90mol%, at least 95mol%, the concentration of 99mol% or 100mol% is configured for forming part or all of dicarboxylic acid component of polyester of the present invention at least. In certain embodiments, can use the polyester with higher amount terephthalic acid (TPA) in order to obtain than the high impact performance. For the purpose of present disclosure, term " terephthalic acid (TPA) " and " dimethyl terephthalate (DMT) " are used interchangeably in this article. In one embodiment, dimethyl terephthalate (DMT) is part or all for the preparation of the dicarboxylic acid component who can be used for polyester of the present invention. In all embodiments, can use 70-100mol%; Or 80-100mol%; Or 90-100mol%; Or 99-100mol%; Or the terephthalic acid (TPA) of 100mol% and/or dimethyl terephthalate (DMT) and/or its mixture.

[0168] except the terephthalic acid residue, the dicarboxylic acid component who can be used for polyester of the present invention can comprise at the most 30mol%, at the most 20mol%, at the most 10mol%, at the most 5mol% or one or more modified aromatic dicarboxylic acids of 1mol% at the most. Another embodiment comprises 0mol% modified aromatic dicarboxylic acids. Therefore, if exist, expect that the amount of one or more modified aromatic dicarboxylic acids can in any above-mentioned endpoint value scope, comprise for example one or more modified aromatic dicarboxylic acids of 0.01-30mol%, 0.01-20 mol%, 0.01-10mol%, 0.01-5mol% or 0.01-1mol%. In one embodiment, can be used for modified aromatic dicarboxylic acids of the present invention and include but not limited to have those of 20 carbon atoms at the most, and they can be linear, para-orientation or symmetrical. The example that can be used for modified aromatic dicarboxylic acids of the present invention includes but not limited to M-phthalic acid, 4,4 '-biphenyl dicarboxylic acid, Isosorbide-5-Nitrae-, 1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid and trans-4,4 '-Stilbene dioctyl phthalate and ester thereof. In one embodiment, M-phthalic acid is the modified aromatic dicarboxylic acids.

[0169] dicarboxylic acid component who can be used for polyester of the present invention can further use at the most 10 mol%, for example at the most 5mol% or at the most one or more of 1mol% contain the aliphatic dicarboxylic acid of 2-16 carbon atom, for example cyclohexane cyclohexanedimethanodibasic, malonic acid, butanedioic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and dodecanedioic acid modification. Some embodiment also can comprise 0.01 mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modification aliphatic dicarboxylic acids. Another embodiment comprises 0 mol% modification aliphatic dicarboxylic acid. Therefore, if exist, expect that the amount of one or more modification aliphatic dicarboxylic acids can in any above-mentioned endpoint value scope, comprise for example 0.01-10mol% and 0.1-10mol%. Total mol% of dicarboxylic acid component is 100mol%.

[0170] modification dicarboxylic acids of the present invention can comprise the indane dioctyl phthalate, for example indane-1,3-dioctyl phthalate and/or phenyl indan dioctyl phthalate. In one embodiment, dicarboxylic acids can be selected from 1,2,3-trimethyl-3-phenyl indan-4 ', 5 '-dioctyl phthalate and 1,1,3-trimethyl-5-carboxyl-3-(4-carboxyl phenyl) indane dioctyl phthalate at least a. For the purposes of the present invention, can use any indane dioctyl phthalate described in the U.S. Patent Application Publication 2006/0004151A1 that is entitled as " Copolymers Containing Indan Moieties and Blends Thereof " of Shaikh of transferring General Electric Company etc. as at least a modification dicarboxylic acids in the scope of the invention; Be incorporated herein U.S. Patent Application Publication 2006/0004151A1 as a reference about wherein said any indane dicarboxylic acid.

[0171] can use the ester of terephthalic acid (TPA) and other modification dicarboxylic acids or their corresponding esters and/or salt to replace dicarboxylic acids. The suitable example of dicarboxylic ester includes but not limited to dimethyl, diethyl, dipropyl, diisopropyl, dibutyl and diphenyl. In one embodiment, described ester is selected from following at least a: methyl, ethyl, propyl group, isopropyl and phenylester.

[0172] cyclohexanedimethanol can be cis, trans or its mixture, and for example cis/trans ratios is 60: 40-40: 60 or cis/trans ratios be 70: 30-30: 70. In another embodiment, the amount of trans-cyclohexanedimethanol can be 20-40mol% for the amount of 60-80mol% cis-cyclohexanedimethanol, wherein the toatl proportion 100mol% of cis and trans cyclohexane dimethanol. In special embodiment, the amount of trans-cyclohexanedimethanol can be 40mol% for the amount of 60mol% cis-cyclohexanedimethanol. In special embodiment, the amount of trans-cyclohexanedimethanol can be 30mol% for the amount of 70mol% cis-cyclohexanedimethanol. Cyclohexanedimethanol any 1,1-, 1,2-, 1,3-, Isosorbide-5-Nitrae-isomers or its mixture may reside in the diol component of the present invention. In one embodiment, can be used for polyester of the present invention and comprise 1,4-CHDM. In another embodiment, can be used for polyester of the present invention and comprise 1,4-CHDM and 1,3-CHDM.

[0173] diol component that can be used for the polyester portion of polymer blend of the present invention can contain 25mol% or still less one or more are not the modification glycol of TMCBD or cyclohexanedimethanol; In one embodiment, can be used for polyester of the present invention and can contain one or more modification glycol less than 15mol%. In another embodiment, can be used for polyester of the present invention and can contain 10mol% or one or more modification glycol still less. In another embodiment, can be used for polyester of the present invention and can contain 5mol% or one or more modification glycol still less. In another embodiment, can be used for polyester of the present invention and can contain 3mol% or one or more modification glycol still less. In another embodiment, can be used for the modification glycol that polyester of the present invention can contain 0mol%. Some embodiment also can comprise 0.01 mol% or more, for example 0.1mol% or more, 1mol% or more, 5mol% or more or 10mol% or more one or more modification glycol. Therefore, if exist, expect that the amount of one or more modification glycol can in any above-mentioned endpoint value scope, comprise for example 0.01-15 mol% and 0.1-10mol%.

[0174] the modification glycol that can be used for polyester of the present invention can represent the glycol outside TMCBD and the cyclohexanedimethanol, and can contain 2-16 carbon atom. The example of suitable modification glycol includes but not limited to ethylene glycol, diethylene glycol (DEG), 1,2-PD, 1,3-PD, neopentyl glycol, BDO, 1,5-PD, 1,6-hexylene glycol, paraxylene glycol, polytetramethylene glycol or its mixture. In one embodiment, the modification glycol is ethylene glycol. In another embodiment, the modification glycol includes but not limited to 1,3-PD and/or Isosorbide-5-Nitrae-butanediol. In another embodiment, get rid of ethylene glycol as the modification glycol. In another embodiment, get rid of 1,3-PD and BDO as the modification glycol. In another embodiment, get rid of NPG as the modification glycol. The polyester and/or the Merlon that can be used for polymer blend of the present invention can comprise 0-10mol%, the residue of one or more branched monomers of 0.01-5 mol%, 0.01-1mol%, 0.05-5mol%, 0.05-1mol% or 0.1-0.7mol% or 0.1-0.5mol% for example, be also referred to as branching agent herein, have 3 or a plurality of carboxyl substituent, hydroxyl substituent or its combination, described content is respectively based on total mole percent of glycol or diacid residues. In certain embodiments, can before the polyester and/or during and/or add afterwards branched monomer or reagent. Therefore being used for polyester of the present invention can be linearity or branching. Merlon also can be linearity or branching. In certain embodiments, can before the polycarbonate polymerization and/or during and/or add afterwards branched monomer or reagent.

[0175] example of branched monomer includes but not limited to polyfunctional acid or polyfunctional alcohol, such as trimellitic acid, trimellitic anhydride, pyromellitic acid dianhydride, trimethylolpropane, glycerine, pentaerythrite, citric acid, tartaric acid, 3-hydroxyl glutaric acid etc. In one embodiment, the branched monomer residue can comprise 0.1-0.7mol% one or more be selected from following at least a residue: trimellitic anhydride, pyromellitic acid dianhydride, glycerine, D-sorbite, 1,2,6-hexanetriol, pentaerythrite, trimethylolethane and/or trimesic acid. Branched monomer can be added in the pet reaction mixture, perhaps with concentrate form and polyester blend, for example such as USP 5,654,347 and 5,696, described in 176, its disclosure about branched monomer is hereby incorporated by.

[0176] uses the glass transition temperature (Tg) that can be used for polyester of the present invention from the TA DSC 2920 of Thermal Analyst Instrument with the determination of scan rate of 20 ℃/min.

[0177] owing to grows (for example greater than 5 minutes) by some flexible chain at 170 ℃ that is used for polyester demonstration of the present invention, can article of manufacture, include but not limited to articles injection-moulded, injection blow molding mechanograph, injection stretch blow mechanograph, cast film, extrusion molding thin plate, extrusion blow molded mechanograph, squeeze base stretch-blow mechanograph and fiber. Thermoformable thin plate is an example by manufacturing goods provided by the invention. Polyester of the present invention can be unbodied or hypocrystalline. In one aspect, be used for some polyester of the present invention and can have lower degree of crystallinity. Be used for some polyester of the present invention and therefore can have essentially amorphous form, represent that this polyester comprises substantially unordered polymer areas.

[0178] in one embodiment, " amorphous " polyester can have 170 ℃ greater than 5 minutes, or 170 ℃ greater than 10 minutes, or at 170 ℃ greater than 50 minutes, or at 170 ℃ of flexible chains greater than 100 minutes. In one embodiment of the invention, this flexible chain at 170 ℃ greater than 1,000 minute. In another embodiment of the invention, the flexible chain that can be used for polyester of the present invention at 170 ℃ greater than 10,000 minutes. The flexible chain of polyester used herein can be measured with the well-known method of those skilled in the art. For example, the flexible chain t of polyester_1/2Can determine over time by the light transmittance of measuring sample on the temperature controlled hot platform by laser instrument and photoelectric detector. This measurement can be by being exposed to temperature T with polymer_maxAnd the temperature that subsequently it is cooled to expect is carried out. Can sample be remained on the temperature of expectation by hot platform subsequently, measure simultaneously transmissivity over time. At first, sample can be visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization. Flexible chain is that light transmittance is the time of a half between initial light transmittance and the final light transmittance. T_maxBe defined as the required temperature of fusing sample crystal region (if having crystal region). Can before flexible chain is measured, sample be heated to T_maxTo nurse one's health this sample. For each composition, absolute T_maxTemperature is different. For example, PCT can be heated to above certain temperature of 290 ℃ with fusion-crystallization zone.

[0179] such as the table 1 of embodiment and shown in Figure 1, improving flexible chain, namely polymer reaches half needed time aspect of its maximum degree of crystallinity, 2,2,4,4-tetramethyl-1, the 3-cyclobutanediol is more effective than other comonomer such as ethylene glycol and M-phthalic acid. By reducing the crystalline rate of PCT, namely improve flexible chain, can be by manufacturings such as methods known in the art such as extrusion molding, injection mouldings based on the amorphous goods of modification PCT. As shown in table 1, these materials can show than the higher glass transition temperature of other modification PCT copolyesters and lower density.

[0180] for certain embodiments of the present invention, polyester of the present invention can show that the combination of toughness and processability improves. For example, unexpectedly, the logarithmic viscosity number that slight reduction can be used for polyester of the present invention obtains the melt viscosity of easier processing, keeps simultaneously the good physical property of polyester, for example toughness and heat resistance.

[0181] content that improves based on cyclohexanedimethanol in the copolyesters of terephthalic acid (TPA), ethylene glycol and cyclohexanedimethanol can improve toughness, and described toughness can be determined by the brittle-ductile transition temperature in the notched izod impact strength test of measuring according to ASTM D256. It is believed that by this toughness that reduces the brittle-ductile transition temperature with cyclohexanedimethanol improve be since in the copolyesters pliability of cyclohexanedimethanol and conformation behavior occur. It is believed that TMCBD is incorporated among the PCT, improved toughness by reducing the brittle-ductile transition temperature, such as the table 2 of embodiment and shown in Figure 2. This is unexpected in the situation of given TMCBD rigidity.

[0182] in one embodiment, be used for the melt viscosity of polyester of the present invention less than 30,000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃. In another embodiment, be used for the melt viscosity of polyester of the present invention less than 20,000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃.

[0183] in one embodiment, be used for the melt viscosity of polyester of the present invention less than 15,000 pools, on the rotation melt rheometer, measure with 1 radian per second (rad/sec) in 290 ℃. In one embodiment, be used for the melt viscosity of polyester of the present invention less than 10,000 pools, on the rotation melt rheometer, measure with 1 radian per second (rad/sec) in 290 ℃. In another embodiment, be used for the melt viscosity of polyester of the present invention less than 6,000 pools, on the rotation melt rheometer, measure with 1 radian per second in 290 ℃. Viscosity take radian per second as unit is relevant with processability. When its processing temperature is measured, typical polymers has the viscosity with 1 radian per second mensuration less than 10,000 pools. Polyester is generally can not be processed more than 290 ℃. Merlon generally can be processed at 290 ℃. Merlon is 7,000 pools 290 ℃ viscosity under typical 12 melt flow of 1 rad/sec.

[0184] in one embodiment, polyester of the present invention goes out superior notch toughness at thick partial display. The described notched izod impact strength of ASTM D256 is to measure a kind of commonsense method of toughness. Can be used for polyester of the present invention and can have one or more following performances. In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 3.2mm (1/8-in) in the impact strength of at least 150J/m (3ft-lb/in) that measures of 10 mil breach; In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 3.2mm (1/8-in) in the notched izod impact strength of at least 400J/m (7.5 ft-lb/in) that measures of 10 mil breach; In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 3.2mm (1/8-in) in the notched izod impact strength of at least 1000J/m (18ft-lb/in) that measures of 10 mil breach. In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 6.4mm (1/4-in) in the notched izod impact strength of at least 150J/m (3ft-lb/in) that measures of 10 mil breach; In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 6.4mm (1/4-in) in the notched izod impact strength of at least 400 J/m (7.5ft-lb/in) that measure of 10 mil breach; In one embodiment, can be used for polyester of the present invention show according to ASTM D256 in 23 ℃ with the thick band sample of 6.4mm (1/4-in) in the notched izod impact strength of at least 1000J/m (18ft-lb/in) that measures of 10 mil breach.

[0185] in another embodiment, with compare in-5 ℃ of notched izod impact strength that 10 mil breach are measured in the thick band sample with 1/8-in according to ASTM D256, when when 0 ℃ is measured, can be used for the increase that some polyester of the present invention can show at least 3% or at least 5% or at least 10% or at least 15% notched izod impact strength. In addition, when 10 mil breach are 0 ℃-30 ℃ measurements in the thick band sample with 1/8-in according to ASTM D256, can be used for some other polyester of the present invention and can show that also plus or minus 5% is with interior notched izod impact strength confining force.

[0186] in another embodiment, with compare in the notched izod impact strength of the uniform temp identical polyester that 10 mil breach are measured in the thick band sample with 1/8-in according to ASTM D256, when according to ASTM D256 in 23 ℃ with 1/4-in when 10 mil breach are measured in the thick band sample, can be used for some polyester of the present invention can be not more than 70% notched izod impact strength confining force by display loss.

[0187] in one embodiment, based on by 10 mil breach in the thick band sample of 1/8-in of ASTM D256 definition, can be used for polyester of the present invention and can show and be lower than 0 ℃ ductile-brittle transition temperature.

[0188] in one embodiment, it can be visually transparent can be used for polyester of the present invention. Term " visually transparent " is defined as in this article that do not exist can perceptible darkness, dim and/or muddy when visual detection. In another embodiment, when polyester and Merlon (including but not limited to bisphenol-a polycarbonate) blend, blend can be visually transparent.

[0189] polyester of the present invention has one or more following performances. In other embodiments, can be used for polyester of the present invention can have less than 50 or less than 20 yellowness index (ASTM D-1925).

[0190] in one embodiment, can be used for polyester of the present invention and/or polymer blend of the present invention and contain or do not contain toner, can have colour L^*、a ^*And b^*, it can use the Inc. by Hunter Associates Lab, Reston, and the Hunter Lab Ultrascan Spectra Colorimeter that Va makes measures. The colour measurement value is the mean value of the value measured at polyester granules or by plate or other article of its injection moulding or extrusion molding. They are by the L of CIE (International Commission on Illumination (International Commission on Illumination)) (translation version)^*a ^*b ^*Colour system is definite, wherein L^*The expression lightness dimension, a^*Represent red/green coordinate, and b^*Expression Huang/blue coordinate. In certain embodiments, the b that can be used for polyester of the present invention^*Value can be for-10 to less than 10, and L^*Value can be 50 to 90. In other embodiments, the b that can be used for polyester of the present invention^*Value can exist with one of following scope :-10 to 9;-10 to 8;-10 to 7;-10 to 6;-10 to 5;-10 to 4;-10 to 3;-10 to 2;-5 to 9;-5 to 8;-5 to 7;-5 to 6;-5 to 5;-5 to 4;-5 to 3;-5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0 to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1 to 5; 1 to 4; 1 to 3; 1 to 2. In other embodiments, the L that can be used for polyester of the present invention^*Value can exist with one of following scope: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60 to 80; 60 to 90; 70 to 80; 79 to 90.

[0191] in one embodiment, can be used at least one that polyester of the present invention can show following density: 23 ℃ of density less than 1.3g/ml; 23 ℃ of density less than 1.2g/ml; 23 ℃ of density less than 1.18g/ml; The density of 23 ℃ of 0.70-1.2g/ml; The density of 23 ℃ of 0.70-1.3g/ml; 23 ℃ of 0.70-are less than the density of 1.2g/ml; The density of 23 ℃ of 0.75-1.2g/ml; 23 ℃ of 0.75-are less than the density of 1.2g/ml; The density of 23 ℃ of 0.80-1.2g/ml; 23 ℃ 0.80-less than the density of 1.2g/ml; The density of 23 ℃ of 0.90-1.2g/ml; The density of 23 ℃ of 1.0-1.2g/ml; The density of 23 ℃ of 1.0-1.3g/ml; The density of 23 ℃ of 1.1-1.2g/ml; The density of 23 ℃ of 1.13-1.3g/ml; The density of 23 ℃ of 1.13-1.2g/ml; The density of 23 ℃ of 0.80-1.18g/ml; 23 ℃ of 0.80-are less than the density of 1.18g/ml; 23 ℃ of 1.0-are less than the density of 1.18g/ml; 23 ℃ of 1.1-are less than the density of 1.18g/ml.

[0192] in some embodiments, use polymer blend of the present invention before melt-processed and/or thermoforming, to minimize and/or get rid of drying steps.

[0193] can have any moisture although can be used for polyester of the present invention, in one embodiment, they can have the moisture of the 0.02-1.0wt% of polyester gross weight before melt-processed.

[0194] in certain embodiments, before melt-processed, be less than 2 hours by conventional method at 100 ℃ of dry polyester of 60-.

[0195] can be used for polyester of the present invention or of the present invention and/or polymer blend and/or method and can comprise at least a heat stabilizer.

[0196] heat stabilizer is the compound of stabilized polyester between polyester manufacturing and/or rear polymerization period, includes but not limited to phosphorus compound, includes but not limited to phosphoric acid, phosphorous acid, phosphonic acids, phosphinic acids, phosphonous acid and various ester and salt. They may reside in and can be used in the polymer blend of the present invention. Described ester can be the ester of alkyl, branched-alkyl, substituted alkyl, two sense alkyl, alkyl ether, aryl and substituted aryl. In one embodiment, the number that is present in the ester group in the specific phosphorus compound can change to the maximum that allows based on the oh group number that is present in the used heat stabilizer at the most from zero.

[0197] its product intended comprising in term " heat stabilizer ". And the interrelate term " product " that uses of heat stabilizer of the present invention refers to heat stabilizer and the polycondensation of any monomer for the preparation of polyester or spawn and the polycondensation between heat stabilizer and other additive types or the product of esterification of esterification.

[0198] in one embodiment, can be used for heat stabilizer of the present invention can be organic compound, for example comprises halogenation or the phosphate of halogenation organic substituent not. Heat stabilizer can comprise the phosphorus compound well known in the art of wide region, for example phosphine, phosphite ester, ortho phosphorous acid ester (phosphinite), phosphinate, phosphinate, phosphonate ester, phosphine oxide and phosphate. The example of heat stabilizer comprises the tricresyl phosphate butyl ester, the tricresyl phosphate ethyl ester, three butoxy ethyl ester of phosphoric acid, phosphoric acid tert-butyl phenyl diphenyl, phosphoric acid 2-ethylhexyl diphenyl, phosphoric acid ethyl dimethyl esters, phosphoric acid isodecyl diphenyl, the tricresyl phosphate Lauryl Ester, Triphenyl phosphate, lindol, tricresyl phosphate (xylyl) ester, phosphoric acid tert-butyl phenyl diphenyl, resorcinol two (di(2-ethylhexyl)phosphate phenylester), the tricresyl phosphate benzyl ester, the phosphoric acid phenylethylester, thion tricresyl phosphate methyl ester, thion phosphoric acid phenylethylester, the methylphosphonic acid dimethyl esters, the methylphosphonic acid diethyl ester, amyl group phosphonic acids diethyl ester, methylphosphonic acid dilauryl ester, the methylphosphonic acid diphenyl, methylphosphonic acid dibenzyl ester, tolyl phosphonic acids diphenyl, tolyl phosphonic acids dimethyl esters, methyl thion phosphonic acids dimethyl esters, the diphenyl phosphonic acid phenylester, the diphenyl phosphonic acid benzyl ester, the diphenyl phosphonic acid methyl ester, the trimethyl phosphine oxide, triphenylphosphine oxide, the tribenzyl phosphine oxide, 4-methyldiphenyl base phosphine oxide, the tricresyl phosphite ethyl ester, the tricresyl phosphite butyl ester, the tricresyl phosphite Lauryl Ester, the tricresyl phosphite phenylester, the tricresyl phosphite benzyl ester, phosphorous acid diethylamino phenyl base ester, phosphorous acid phenyl dimethyl esters, phosphorous acid benzyl dimethyl ester, methyl phosphonous acid dimethyl esters, amyl group phosphonous acid diethyl ester, methyl phosphonous acid diphenyl, methyl phosphonous acid dibenzyl ester, tolyl phosphonous acid dimethyl esters, dimethyl ortho phosphorous acid methyl ester, diethyl ortho phosphorous acid methyl ester, diphenyl ortho phosphorous acid phenylester, diphenyl ortho phosphorous acid methyl ester, diphenyl ortho phosphorous acid benzyl ester, triphenylphosphine, tribenzyl phosphine and methyldiphenyl base phosphine. In one embodiment, get rid of in triphenylphosphine oxide can be used for polyester of the present invention as preparation the method and the heat stabilizer in the polymer blend of the present invention.

[0199] in one embodiment, can be used for heat stabilizer of the present invention can be any aforementioned acid based on phosphorus, and wherein one or more hydrogen atoms of acid compound (with oxygen or phosphorus atoms bonding) are replaced by aryl that alkyl, branched-alkyl, substituted alkyl, alkyl ether, substituted dialkyl ether, alkyl-aryl, alkyl replace, aryl, substituted aryl and composition thereof. In another embodiment, can be used for heat stabilizer of the present invention and include but not limited to above-mentioned compound, wherein the hydrogen atom of the oxygen atom bonding of at least one and this compound is replaced by metal ion or ammonium ion.

[0200] ester can comprise alkyl, branched-alkyl, substituted alkyl, alkyl ether, aryl and/or substituted aryl group. Ester also can have at least one alkyl group and at least one aromatic yl group. The number that is present in the ester group in the specific phosphorus compound can change to the maximum that allows based on the oh group number that is present on the used phosphorus compound at the most from zero. For example, alkylphosphonate can comprise phosphoric acid one-, two-and three-Arrcostab is one or more; Aryl phosphate comprise phosphoric acid one-, two-and three-aryl ester is one or more; And alkylphosphonate and/or aryl phosphate also include but not limited to have the mixed phosphate alkyl aryl ester of at least one alkyl and an aryl.

[0201] in one embodiment, can be used for alkyl, aryl or mixed alkyl aryl ester or the part ester that heat stabilizer of the present invention includes but not limited to phosphoric acid, phosphorous acid, phosphinic acids, phosphonic acids or phosphonous acid. The alkyl or aryl group can comprise one or more substituting groups.

[0202] on the one hand, can be used for phosphorus compound of the present invention and comprise at least a heat stabilizer, its product and composition thereof, it is selected from and replaces or the aryl phosphite Arrcostab of unsubstituted alkylphosphonate, replacement or unsubstituted aryl phosphate, replacement or unsubstituted mixed phosphate alkyl aryl ester, diphosphites, phosphate, phosphine oxide and mixing at least a. Phosphate comprises that wherein phosphoric acid is by fully esterification or the only esterified ester of part.

[0203] in one embodiment, for example, can be used for heat stabilizer of the present invention and can comprise at least a phosphate.

[0204] on the one hand, can be used for phosphorus compound of the present invention and comprise at least a heat stabilizer, its product and composition thereof, it is selected from and replaces or the replacement of unsubstituted alkylphosphonate, replacement or unsubstituted aryl phosphate, mixing or unsubstituted alkyl aryl phosphate at least a. Phosphate comprises that wherein phosphoric acid is by fully esterification or the only esterified ester of part.

[0205] in one embodiment, for example, can be used for heat stabilizer of the present invention and can comprise at least a phosphate.

[0206] in another embodiment, can be used for alkyl aryl phosphate and/or its mixture that phosphate of the present invention can include but not limited to alkylphosphonate, aryl phosphate, mixing.

[0207] in certain embodiments, can be used for phosphate of the present invention is that wherein the group on the phosphate comprises those of alkyl, alkoxyalkyl, phenyl or substituted-phenyl group. These phosphates are commonly referred to alkyl acid phosphate and/or aryl ester in this article. Some preferred embodiment comprises the mixture of trialkylphosphate, triaryl phosphate, alkyl acid phosphate diaryl ester, di(2-ethylhexyl)phosphate alkyl aryl ester and this phosphate, wherein alkyl group is preferably those that comprise 2-12 carbon atom, and aromatic yl group is preferably phenyl.

[0208] representational alkyl and branched-alkyl group are preferably those that comprise 1-12 carbon atom, include but not limited to ethyl, propyl group, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl group, decyl and dodecyl. The alkyl group that replaces includes but not limited to comprise at least a those of hydroxy-acid group and ester thereof, oh group, amino group, oxo group etc.

[0209] alkyl-aromatic yl group of representational alkyl-aryl and replacement comprises 1-12 carbon atom for moieties wherein, and aromatic yl group is phenyl or substituted-phenyl (wherein such as the hydrogen on any carbon location on the group substituted benzene ring of alkyl, branched-alkyl, aryl, hydroxyl etc.) those. Preferred aromatic yl group comprises phenyl or substituted-phenyl, wherein such as the hydrogen on any carbon location on the group substituted benzene ring of alkyl, branched-alkyl, aryl, hydroxyl etc.

[0210] in one embodiment, the phosphate that can be used as heat stabilizer of the present invention includes but not limited to di(2-ethylhexyl)phosphate butyl phenyl ester, Triphenyl phosphate, lindol, tricresyl phosphate butyl ester, tricresyl phosphate-2-ethylhexyl, tricresyl phosphate octyl group ester and/or its mixture, particularly including the mixture of tricresyl phosphate butyl ester and lindol and the mixture of phosphoric acid isocetyl diphenyl and phosphoric acid 2-ethylhexyl diphenyl.

[0211] in one embodiment, the phosphate that can be used as heat stabilizer of the present invention includes but not limited to following at least a: the alkyl aryl phosphate of trialkylphosphate, triaryl phosphate, alkyl acid phosphate diaryl ester and mixing.

[0212] in one embodiment, the phosphate that can be used as heat stabilizer of the present invention includes but not limited to following at least a: the alkyl aryl phosphate of triaryl phosphate, alkyl acid phosphate diaryl ester and mixing.

[0213] in one embodiment, the phosphate that can be used as heat stabilizer of the present invention includes but not limited to following at least a: the alkyl aryl phosphate of triaryl phosphate and mixing. In one embodiment, at least a heat stabilizer includes but not limited to triaryl phosphate, for example Triphenyl phosphate. In one embodiment, at least a heat stabilizer includes but not limited to Merpol A.

[0214] in one embodiment, at least a heat stabilizer includes but not limited to triaryl phosphate, for example Triphenyl phosphate. In one embodiment, at least a heat stabilizer includes but not limited to Merpol A. In one embodiment, at least aly can be used for heat stabilizer of the present invention and include but not limited to that Triphenyl phosphate and Merpol A's is at least a. Merpol A is the phosphate of buying from Stepan Chemical Co and/or E.I.duPont de Nemours﹠Co.. The CAS number of registration that it is believed that Merpol A is CAS registration #37208-27-8.

[0215] in one embodiment, polymer blend of the present invention and/or method can comprise phosphoric acid 2-ethylhexyl diphenyl.

[0216] in one embodiment, polymer blend of the present invention and/or method can comprise phosphoric acid 2-ethylhexyl diphenyl.

[0217] in one embodiment, can be used for phosphorus compound of the present invention and include but not limited at least a diphosphites.

[0218] in one embodiment, can be used for phosphorus compound of the present invention and include but not limited at least a diphosphites, it comprises 2,4,8,10-, four oxa-s-3,9-two phospha spiral shell [5.5] hendecane structures, for example Weston 619 (GE Specialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0219] in one embodiment, can be used for phosphorus compound of the present invention and comprise at least a phosphine oxide, for example triphenylphosphine oxide.

[0220] in one embodiment, can be used for the phosphorous acid alkyl aryl ester that phosphorus compound of the present invention comprises at least a mixing, for example two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, be also referred to as Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0221] in one embodiment, any method for the preparation of polymer blend and/or polyester as herein described comprises at least a phosphorus compound as herein described.

[0222] in one embodiment, any method for the preparation of any polymer blend and/or polyester as herein described can comprise at least a diphosphites.

[0223] in one embodiment, any method for the preparation of any polymer blend and/or polyester as herein described can comprise at least a diphosphites, it comprises 2,4,8,10-, four oxa-s-3,9-two phospha spiral shell [5.5] hendecane structures, for example Weston 619 (GE Specialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0224] in one embodiment, any method for the preparation of any polymer blend and/or polyester as herein described can comprise at least a phosphine oxide, for example triphenylphosphine oxide.

[0225] in one embodiment, any method for the preparation of any polymer blend and/or polyester as herein described can comprise the phosphorous acid alkyl aryl ester of at least a mixing, for example two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, be also referred to as Doverphos S-9228 (Dover Chemicals, CAS#154862-43-8).

[0226] when phosphorus being added to polyester of the present invention and/or polymer blend and/or prepare in the method for polyester, it is with the form of phosphorus compound as herein described, and for example at least a phosphate, at least a diphosphites, at least a phosphatic form are added. Adding the amount of the phosphorus compound (for example at least a diphosphites) in polyester of the present invention and/or polymer blend of the present invention and/or the method for the present invention to can measure with the phosphorus atoms form that is present in the final polyester, for example measures with ppm by weight.

The amount of the heat stabilizer that [0227] adds during polymerization or rear the manufacturing can include but not limited to: 1-5000ppm, 1-1000ppm, 1-900ppm, 1-800ppm, 1-700ppm, 1-600ppm, 1-500ppm, 1-400ppm, 1-350ppm, 1-300ppm, 1-250 ppm, 1-200ppm, 1-150ppm, 1-100ppm, 10-5000ppm, 10-1000 ppm, 10-900ppm, 10-800ppm, 10-700ppm, 10-600ppm, 10-500 ppm, 10-400ppm, 10-350ppm, 10-300ppm, 10-250ppm, 10-200 ppm, 10-150ppm, 10-100ppm is based on the gross weight of polymer blend.

[0228] in one embodiment, the phosphorus compound of the present invention that between polymerization period, adds (diphosphites for example, phosphate etc.) amount is selected from following amount: 1-5000ppm, 1-1000 ppm, 1-900ppm, 1-800ppm, 1-700ppm, 1-600ppm, 1-500ppm, 1-400ppm, 1-350ppm, 1-300ppm, 1-250ppm, 1-200ppm, 1-150 ppm, 1-100ppm, 1-60ppm, 2-5000ppm, 2-1000ppm, 2-900ppm, 2-800ppm, 2-700ppm, 2-600ppm, 2-500ppm, 2-400ppm, 2-350 ppm, 2-300ppm, 2-250ppm, 2-200ppm, 2-150ppm, 2-100ppm, 2-60ppm, 2-20ppm, 3-5000ppm, 3-1000ppm, 3-900ppm, 3-800 ppm, 3-700ppm, 3-600ppm, 3-500ppm, 3-400ppm, 3-350ppm, 3-300ppm, 3-250ppm, 3-200ppm, 3-150ppm, 3-100ppm, 3-60 ppm, 3-20ppm, 4-5000ppm, 4-1000ppm, 4-900ppm, 4-800ppm, 4-700ppm, 4-600ppm, 4-500ppm, 4-400ppm, 4-350ppm, 4-300 ppm, 4-250ppm, 4-200ppm, 4-150ppm, 4-100ppm, 4-60ppm, 4-20ppm, 5-5000ppm, 5-1000ppm, 5-900ppm, 5-800ppm, 5-700 ppm, 5-600ppm, 5-500ppm, 5-400ppm, 5-350ppm, 5-300ppm, 5-250ppm, 5-200ppm, 5-150ppm, 5-100ppm, 5-60ppm, 5-20 ppm, 6-5000ppm, 6-1000ppm, 6-900ppm, 6-800ppm, 6-700ppm, 6-600ppm, 6-500ppm, 6-400ppm, 6-350ppm, 6-300ppm, 6-250 ppm, 6-200ppm, 6-150ppm, 6-100ppm, 6-60ppm, 6-20ppm, 7-5000ppm, 7-1000ppm, 7-900ppm, 7-800ppm, 7-700ppm, 7-600 ppm, 7-500ppm, 7-400ppm, 7-350ppm, 7-300ppm, 7-250ppm, 7-200ppm, 7-150ppm, 7-100ppm, 7-60ppm, 7-20ppm, 8-5000 ppm, 8-1000ppm, 8-900ppm, 8-800ppm, 8-700ppm, 8-600ppm, 8-500ppm, 8-400ppm, 8-350ppm, 8-300ppm, 8-250ppm, 8-200 ppm, 8-150ppm, 8-100ppm, 8-60ppm, 8-20ppm, 9-5000ppm, 9-1000ppm, 9-900ppm, 9-800ppm, 9-700ppm, 9-600ppm, 9-500 ppm, 9-400ppm, 9-350ppm, 9-300ppm, 9-250ppm, 9-200ppm, 9-150ppm, 9-100ppm, 9-60ppm, 9-20ppm, 10-5000ppm, 10-1000ppm, 10-900ppm, 10-800ppm, 10-700ppm, 10-600ppm, 10-500ppm, 10-400ppm, 10-350ppm, 10-300ppm, 10-250ppm, 10-200ppm, 10-150ppm, 10-100ppm, 10-60ppm, 10-20ppm, 50-5000ppm, 50-1000ppm, 50-900ppm, 50-800ppm, 50-700ppm, 50-600ppm, 50-500ppm, 50-400ppm, 50-350ppm, 50-300ppm, 50-250ppm, 50-200ppm, 50-150ppm, 50-100ppm, 50-80ppm, 100-5000ppm, 100-1000ppm, 100-900ppm, 100-800ppm, 100-700 ppm, 100-600ppm, 100-500ppm, 100-400ppm, 100-350ppm, 100-300ppm, 100-250ppm, 100-200ppm, 100-150ppm, 150-5000 ppm, 150-1000ppm, 150-900ppm, 150-800ppm, 150-700ppm, 150-600ppm, 150-500ppm, 150-400ppm, 150-350ppm, 150-300ppm, 150-250ppm, 150-200ppm, 200-5000ppm, 200-1000ppm, 200-900ppm, 200-800ppm, 200-700ppm, 200-600ppm, 200-500ppm, 200-400ppm, 200-350ppm, 200-300ppm, 200-250ppm, 250-5000 ppm, 250-1000ppm, 250-900ppm, 250-800ppm, 250-700ppm, 250-600ppm, 250-500ppm, 250-400ppm, 250-350ppm, 250-300ppm, 500-5000ppm, 300-1000ppm, 300-900ppm, 300-800ppm, 300-700ppm, 300-600ppm, 300-500ppm, 300-400ppm, 300-350ppm, 350-5000ppm, 350-1000ppm, 350-900ppm, 350-800ppm, 350-700ppm, 350-600ppm, 350-500ppm, 350-400ppm based on the gross weight of polymer blend, and measures with the phosphorus atoms form in the final polyester.

[0229] the suitable catalyst for the preparation of the inventive method that can be used for polyester of the present invention comprises at least a tin compound. Polymer blend of the present invention also can comprise at least a tin compound that can be used for the inventive method. Other catalyst can be used for the present invention with at least a tin compound combination. Other catalyst can include but not limited to based on titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminium compound and contain lithium hydroxide or the catalyst of the aluminium compound of NaOH. In one embodiment, catalyst can be the combination of at least a tin compound and at least a titanium compound.

[0230] amount of catalyst can be between 10ppm-20,000ppm, or 10ppm-10,000 ppm, or 10ppm-5,000ppm, or 10ppm-1,000ppm, or 10ppm-500 ppm, or 10ppm-300ppm, or 10ppm-250ppm are based on catalyst metals and based on the weight of final polymer. Described method can be carried out with intermittence or continuation method. In one embodiment, catalyst is tin compound. In one embodiment, catalyst only is tin compound. In one embodiment, tin compound can be used for esterification or polycondensation reaction or this two kinds of reactions. In another embodiment, catalyst only is the tin compound for esterification. Usually, in one embodiment, tin compound catalyst uses with the amount of about 0.005%-about 0.2%, based on the weight of dicarboxylic acids or dicarboxylic ester. Usually, in one embodiment, the element tin that exists as residue in polyester should be less than about 700ppm, based on the gross weight of polyester based on weight polyester.

[0231] when tin being added to polyester of the present invention and/or polymer blend and/or prepare in the method for polyester, its form with tin compound is added in the method for preparing polyester. Adding the amount of the tin compound in polyester of the present invention and/or polymer blend of the present invention and/or the method for the present invention to can measure with the tin atom form that is present in the final polyester, for example measures with ppm by weight.

[0232] in another embodiment, catalyst only is the tin compound for esterification, and its amount is 10ppm-20,000ppm, or 10-10,000ppm, or 10-5000ppm, or 10-4500ppm, or 10-4000ppm, or 10-3500ppm, or 10-3000ppm, or 10-2500ppm, or 10-2000ppm, or 10-1500ppm, or 10-1000ppm, or 10-500ppm, or 10-300ppm, or 10-250ppm, or 15ppm-20,000 ppm, or 15-10,000ppm, or 15-5000ppm, or 15-4500ppm, or 15-4000ppm, or 15-3500ppm, or 15-3000ppm, or 15-2500ppm, or 15-2000ppm, or 15-1500ppm, or 15-1000ppm, or 15-500ppm, or 15-400ppm, or 15-300ppm, or 15-250ppm, or 20ppm-20,000ppm, or 20-10,000ppm, or 20-5000ppm, or 20-4500ppm, or 20-4000 ppm, or 20-3500ppm, or 20-3000ppm, or 20-2500ppm, or 20-2000 ppm, or 20-1500ppm, or 20-1000ppm, or 20-500ppm, or 20-300 ppm, or 20-250ppm 25ppm-20,000ppm, or 25-10,000ppm, or 25-5000ppm, or 25-4500ppm, or 25-4000ppm, or 25-3500ppm, or 25-3000ppm, or 25-2500ppm, or 25-2000ppm, or 25-1500ppm, or 25-1000ppm, or 25-500ppm, or 25-400ppm, or 25-300ppm, or 25-250ppm, or 30ppm-20,000ppm, or 30-10,000ppm, or 30-5000 ppm, or 30-4500ppm, or 30-4000ppm, or 30-3500ppm, or 30-3000 ppm, or 30-2500ppm, or 30-2000ppm, or 30-1500ppm pr 30-1000 ppm, or 30-500ppm, or 30-300ppm, or 30-250ppm, or 35ppm-20,000ppm, or 35-10,000ppm, or 35-5000ppm, or 35-4500ppm, or 35-4000ppm, or 35-3500ppm, or 35-3000ppm, or 35-2500ppm, or 35-2000ppm, or 35-1500ppm, or 35-1000ppm, or 35-500ppm, or 35-300ppm, or 35-250ppm, or 40ppm-20,000ppm, or 40-10,000 ppm, or 40-5000ppm, or 40-4500ppm, or 40-4000ppm, or 40-3500 ppm, or 40-3000ppm, or 40-2500ppm, or 40-2000ppm, or 40-1500 ppm, or 40-1000ppm, or 40-500ppm, or 40-300ppm, or 40-250 ppm, or 40-200ppm, or 45ppm-20,000ppm, or 45-10,000ppm, or 45-5000ppm, or 45-4500ppm, or 45-4000ppm, or 45-3500ppm, or 45-3000ppm, or 45-2500ppm, or 45-2000ppm, or 45-1500ppm, or 45-1000ppm, or 45-500ppm, or 45-300ppm, or 45-250ppm, or 50ppm-20,000ppm, or 50-10,000ppm, or 50-5000ppm, or 50-4500ppm, or 50-4000ppm, or 50-3500ppm, or 50-3000ppm, or 50-2500ppm, or 50-2000ppm, or 50-1500ppm, or 50-1000ppm, or 50-500ppm, or 50-300ppm, or 50-250ppm, or 50-200ppm, or 50-150ppm, or 50-125ppm, based on the weight of final polyester, measure with the tin atom form in the final polyester.

[0233] in another embodiment, polyester of the present invention can use at least a tin compound to prepare as catalyst. For example, referring to USP 2,720,507, wherein the part about tin catalyst is incorporated herein by reference. These catalyst are the tin compounds that comprise at least one organic group. These catalyst comprise divalence or tetravalent tin both, it has following general formula:

A.M ₂(Sn(OR) ₄)

B.MH(Sn(OR) ₄)

C.M′(Sn(OR) ₄)

D.M′(HSn(OR) ₄) ₂

E.M ₂(Sn(OR) ₆)

F.MH(Sn(OR) ₆)

G.M′(Sn(OR) ₆)

H.M′(HSn(OR) ₆) ₂

I.Sn(OR) ₂

J.Sn(OR) ₄

K.SnR′ ₂

L.SnR′ ₄

M.R′ ₂SnO

Wherein M is alkali metal; for example lithium, sodium or potassium; M ' is alkaline-earth metal; for example Mg, Ca or Sr; each R representative comprises the alkyl of 1-8 carbon atom; the representative of each R ' group is selected from by the alkyl that comprises 1-8 carbon atom (being the R group) and comprises the substituting group of those groups that the aromatic yl group (groups such as phenyl, tolyl, benzyl, phenethyl) of the benzene series of 6-9 carbon atom forms, and Ac represents derived from the organic acid carboxyl groups that comprises 2-18 carbon atom (such as acetyl group, bytyry, lauroyl, benzoyl, stearyl etc.).

[0234] the novel dual metal alkoxide catalysis can be such as Meerwein, Ann.476,113 (1929) described preparations. As by shown in the Meerwein, these catalyst are not only the mixture of two kinds of metal alkoxides. They are to have the salt-like structured compound of making clear. These are by with the compound shown in the following formula A-H. Can be by being similar to by the work embodiment of Meerwein proposition and the program preparation of method without special those compounds described of Meerwein.

[0235] other tin compound also can prepare by various methods such as described those methods of following document:

About the preparation of diaryltin dihalide (formula P) referring to Ber.62,996 (1929); J.Am. Chem.Soc.49,1369 (1927). About the preparation of diaryltin dihalide (formula P) referring to J.Am. Chem.Soc.47,2568 (1925); C.A.41,90 (1947). About the preparation of oxidation diaryltin (formula M) referring to J.Am.Chem.Soc.48,1054 (1926). About the preparation of four tin aryl compounds (formula K) referring to C.A.32,5387 (1938). About the preparation of pure tin (formula J) referring to C.A.24,586 (1930). About the preparation of alkyl tin salt (formula Q) referring to C.A.31,4290. About the preparation of Alkyzin compound (formula K and L) referring to C.A.35,2470 (1941); C.A.33,5357 (1939). About the preparation of the alkylaryl tin (formula K and L) that mixes referring to C.A.31,4290 (1937); C.A. 38,331 (1944). About the preparation of other tin compound that is not covered by these citing documents referring to " Die Chemie der Metal-Organischen Verbindungen. ", Krause and V.Grosse, Berlin publishes, 1937, Gebroder-Borntrager.

[0236] pure tin (formula I and J) and bimetallic alkoxide (formula A-H) comprise the R substituting group, and this substituting group can represent straight chain and branched alkyl group, such as diethylate, tetramethyl alkoxide, four butylates, four tert butoxides, four hexanol salt etc.

[0237] alkyl derivative (formula K and L) comprises and one or morely is connected in the alkyl group of tin atom, such as dibutyl tin, dihexyl tin, tert-butyl group tin, tetraethyl tin, tetramethyl tin, dioctyl tin etc. by direct C-Sn key. Can replace with oxygen atom for two of the tetraalkyl group, form the compound with formula M, i.e. cacodyl oxide base tin, tin diethyl oxide, dibutyltin oxide, oxidation diheptyl tin etc. In one embodiment, tin catalyst comprises cacodyl oxide base tin.

[0238] by being reacted, oxidation dialkyl tin and alkali metal alcoholates form the compound (this compound is useful especially catalyst) with formula N in alcoholic solution, such as making dibutyltin oxide and caustic alcohol reaction etc. can form complex compound. This formula is intended the described product of representative. The tin compound that comprises alkyl and alkoxy base also is useful catalyst (seeing formula O), such as diethanol tin diethyl, two butanols dibutyl tins, dimethanol dihexyl tin etc.

[0239] salt derived from oxidation dialkyl tin and carboxylic acid or hydrochloric acid reaction also is valuable especially as catalyst; See formula P and Q. The example of these catalyzing and condensing agent comprises dibutyltin diacetate, two butyric acid tin diethyls, dibutyl tin laurate, dibenzoic acid stannous methide, dichloride dibutyl tin, tin diethyl dichloride, dichloride dioctyl tin, distearyl acid dihexyl tin etc.

[0240] can prepare the tin compound with formula K, L and M, wherein one or more R ' groups represent the aromatic yl group of benzene series, such as phenyl, tolyl, benzyl etc. Example comprises stannous phenide, tetraphenyltin, diphenyl dibutyl tin, xylyl tin diethyl, diphenyl tin oxide, Dibenzyltin, tetrabenzyl tin, oxidation two ([B-phenylethyl) tin, oxidation Dibenzyltin etc.

[0241] example that can be used for catalyst of the present invention includes but not limited to following one or more: three-2 ethyl hexanoic acid butyl tin, dibutyltin diacetate, dibutyltin oxide and cacodyl oxide base tin.

[0242] in one embodiment, can be used for catalyst of the present invention and include but not limited to following one or more: three-2 ethyl hexanoic acid butyl tin, dibutyltin diacetate, dibutyltin oxide and cacodyl oxide base tin.

[0243] method of using catalyst based on tin to prepare polyester is known and is recorded among the above-mentioned USP 2,720,507.

[0244] polyester portion that can be used for polymer blend of the present invention can be passed through the known in the literature method, for example passes through the homogeneous solution method, passes through the ester-interchange method in the melt and pass through two-phase interface legal system standby. Suitable method includes but not limited to that one or more dicarboxylic acids and one or more glycol react the step of the time that is enough to form polyester under the pressure of 100 ℃-315 ℃ temperature and 0.1-760mmHg. Referring to USP 3,772,405 about preparing the method for polyester, is incorporated herein about the disclosure of this method as a reference.

[0245] polyester generally can prepare by following process: in the presence of tin catalyst as herein described, during condensation raise until under about 225-310 ℃ the high temperature gradually, under inert atmosphere, condensation dicarboxylic acids or dicarboxylic ester and glycol, and during the later stage of condensation, under low pressure carry out condensation, as the further details of the USP 2,720,507 that is hereby incorporated by is described.

[0246] on the other hand, the present invention relates to prepare the method for copolyesters of the present invention. In one embodiment, the method relates to the copolyesters that preparation comprises terephthalic acid (TPA), TMCBD and 1,4-CHDM. The method may further comprise the steps:

(A) in the presence of at least a tin catalyst and at least a phosphorus compound, the time that the mixture that comprises the monomer that can be used for polyester of the present invention in 250 ℃ of heating of 150-is enough to produce initial polyester;

(B) by heating 1-6 hour and the product of condensation polymerization step (A) at 240-320 ℃; With

(C) remove any unreacted glycol.

[0247] reaction time that is used for esterif iotacation step (A) depends on the raw materials components mole ratio of selected temperature, pressure and glycol and dicarboxylic acids.

[0248] in one embodiment, step (A) can be carried out until 50wt% or more TMCBD react. Step (A) can be carried out under the pressure of 0psig-100psig. And can be used for the interrelate term " product " that uses of any catalyst of the present invention and refer to catalyst and the polycondensation of any monomer for the preparation of polyester or spawn and the polycondensation between catalyst and other additive types or the product of esterification of esterification.

[0249] typically, step (B) and (C) can carry out simultaneously. These steps can be undertaken by methods known in the art, for example by reactant mixture being placed 0.002psig to subatmospheric pressure, perhaps pass through at mixture blowing up hot nitrogen.

[0250] in one embodiment, the present invention includes a kind of method for the preparation of can be used for any polyester of the present invention, comprise the following steps:

(I) be selected under at least one temperature of 150 ℃-200 ℃, be selected from a kind of mixture of heating under at least one pressure of 0psig-70psig scope, wherein said mixture comprises:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(ii) 0-30mol%'s has an at the most aromatic dicarboxylic acid residue of 20 carbon atoms; With

(iii) 0-10mol%'s has an at the most aliphatic dicarboxylic acid residue of 16 carbon atoms; With

(b) diol component comprises:

(i) the TMCBD residue of 1-99mol%; With

(ii) the cyclohexanedimethanol residue of 1-99mol%;

Diol component/the dicarboxylic acid component's who wherein adds in step (I) mol ratio is 1.0-1.5/1.0;

(i) at least a catalyst, it comprises at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminium compound and contain lithium hydroxide or the catalyst of the aluminium compound of NaOH;

(II) at 230 ℃-320 ℃, under at least one pressure of final pressure to the 0.02 holder absolute pressure scope that is selected from step (I) product 1-6 hour of heating steps (I), form final polyester;

Wherein total mol% of the dicarboxylic acid component of final polyester is 100mol%; Wherein total mol% of the diol component of final polyester is 100mol%.

[0251] in one embodiment, the present invention includes a kind of method for the preparation of can be used for any polyester of the present invention, comprise the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) the TMCBD residue of 1-99mol%; With

(ii) the cyclohexanedimethanol residue of 1-99mol%;

The mixture in the heating steps (I) in the presence of at least a catalyst wherein, described catalyst comprise at least a tin compound and optional at least aly be selected from titanium, gallium, zinc, antimony, cobalt, manganese, magnesium, germanium, lithium, aluminium compound and contain lithium hydroxide or the catalyst of the aluminium compound of NaOH; With

Wherein total mol% of the dicarboxylic acid component of final polyester is 100mol%;

Wherein total mol% of the diol component of final polyester is 100mol%.

At least a phosphorus compound wherein, for example at least a phosphate is added to step (I), step (II) and/or step (I) and (II) among both; With

Wherein add phosphorus compound, for example to cause in can be used for final polyester of the present invention total tin atom and the weight ratio of total phosphorus atoms be 2-10:1 at least a phosphate.

[0252] for example, in front in two paragraphs, can be in step of the present invention (I), (II) and/or step (I) and (II) add at least a phosphorus compound among both. In one embodiment, in step (I), add phosphorus compound. Phosphorus compound can comprise for example at least a phosphate.

[0253] in can be used for preparing any method that can be used for polyester of the present invention, at least a heat stabilizer, its product and composition thereof can be added during esterification, polycondensation or both, and/or can add between rear polymerization period. In one embodiment, the heat stabilizer that can be used for any method of the present invention can add during esterification. In one embodiment, if heat stabilizer adds after esterification and polycondensation, then its addition of gross weight based on final polyester is 1-2wt%. In one embodiment, heat stabilizer can comprise at least a phosphorus compound of the present invention that can be used for. In one embodiment, heat stabilizer can comprise at least a phosphate. In one embodiment, heat stabilizer can comprise at least a phosphorus compound that adds during esterif iotacation step. In one embodiment, heat stabilizer can comprise at least a phosphate that for example adds during esterif iotacation step.

[0254] in one embodiment, it is believed that when at least a heat stabilizer that comprises at least a phosphorus compound as herein described uses during the method for preparation according to polyester of the present invention, polyester can more easily prepare and at least a following state can not occur: foaming, splay mark form, color forms, foams, emits gas and unstable melt liquid level, i.e. the fluctuation of polyester or production of polyester and process systems. In another embodiment, it is believed that at least a method of the present invention provides in the situation that above-mentioned at least a predicament can not occur easier a large amount of productions to can be used for the method (for example pilot-scale and/or industrial production) of polyester of the present invention.

[0255] term used herein " in a large number " comprises surpassing the amount that can be used for polyester of the present invention of 100 pounds amount production. In one embodiment, term used herein " in a large number " comprises surpassing the amount that can be used for polyester of the present invention of 1000 pounds amount production.

[0256] on the one hand, preparing the method that can be used for polyester of the present invention can comprise intermittently or continuation method.

[0257] on the one hand, prepare the method that can be used for polyester of the present invention and can comprise continuation method.

[0258] it is believed that preparation can be used for any method of polyester of the present invention can be for the preparation of can be used for any polyester of the present invention.

[0259] reaction time of esterif iotacation step (I) is depended on the raw materials components mole ratio of selected temperature, pressure and glycol and dicarboxylic acids.

[0260] in one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 20 holder absolute pressures-0.02 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 10 holder absolute pressures-0.02 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 5 holder absolute pressures-0.02 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 3 holder absolute pressures-0.02 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 20 holder absolute pressures-0.1 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 10 holder absolute pressures-0.1 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 5 holder absolute pressures-0.1 holder absolute pressures; In one embodiment, the pressure that is used for the step (II) of any method of the present invention comprises at least one pressure that is selected from 3 holder absolute pressures-0.1 holder absolute pressures.

[0261] in one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.0-1.5/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.5/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.3/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.2/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.15/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.10/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.5/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.3/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.2/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.15/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.03-1.10/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.5/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.3/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.2/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.05-1.15/1.0; In one embodiment, the diol component/dicarboxylic acid component's who adds in the step (I) of any method of the present invention mol ratio is 1.01-1.10/1.0.

[0262] in for the preparation of any method embodiment that can be used for polyester of the present invention, can be 1-5 hour the heat time heating time of step (II), or 1-4 hour, or 1-3 hour, or 1.5-3 hour, or 1-2 hour. In one embodiment, can be 1.5-3 hours the heat time heating time of step (II).

[0263] in one embodiment, adding in the methods of the invention phosphorus compound, can to cause in can be used for final polyester of the present invention total tin atom and the weight ratio of total phosphorus atoms be 2-10: 1. In one embodiment, in described method, add phosphorus compound and can cause that the weight ratio of total tin atom and total phosphorus atoms is 5-9 in final polyester: 1. In one embodiment, in described method, add phosphorus compound and can cause that the weight ratio of total tin atom and total phosphorus atoms is 6-8 in final polyester: 1. In one embodiment, in described method, add phosphorus compound and can cause that the weight ratio of total tin atom and total phosphorus atoms is 7: 1 in final polyester. For example, being present in tin atom in the final polyester and the weight of phosphorus atoms can measure with ppm, and can cause that the weight ratio of total tin atom and total phosphorus atoms is any above-mentioned weight ratio in final polyester.

[0264] in one embodiment, the amount of tin atom can be 15-400ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0265] in one embodiment, the amount of tin atom can be 25-400ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0266] in one embodiment, the amount of tin atom can be 40-200ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0267] in one embodiment, the amount of tin atom can be 50-125ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0268] in one embodiment, the amount of phosphorus atoms can be 1-100ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0269] in one embodiment, the amount of phosphorus atoms can be 4-60ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0270] in one embodiment, the amount of phosphorus atoms can be 6-20ppm in can be used for final polyester of the present invention, based on the weight of final polyester.

[0271] in one embodiment, the amount of phosphorus atoms can be 1-100ppm in can be used for final polyester of the present invention, and based on the weight of final polyester, and the amount of tin atom can be 15-400ppm in final polyester, based on the weight of final polyester.

[0272] in one embodiment, the amount of phosphorus atoms can be 1-100ppm in can be used for final polyester of the present invention, and based on the weight of final polyester, and the amount of tin atom can be 25-400ppm in final polyester, based on the weight of final polyester.

[0273] in one embodiment, the amount of phosphorus atoms can be 4-60ppm in can be used for final polyester of the present invention, and based on the weight of final polyester, and the amount of tin atom can be 40-200ppm in final polyester, based on the weight of final polyester.

[0274] in one embodiment, the amount of phosphorus atoms can be 6-20ppm in can be used for final polyester of the present invention, and based on the weight of final polyester, and the amount of tin atom can be 50-125ppm in final polyester, based on the weight of final polyester.

[0275] the invention further relates to the polymer blend that is prepared by said method.

[0276] the invention further relates to blend polymer. This blend comprises:

(a) at least a above-mentioned polyester of 5-95wt%; With

(b) at least a polymers compositions of 5-95wt%.

[0277] the suitable example of polymers compositions includes but not limited to nylon, is different from polyester as herein described, polyamide is such as the ZYTEL from DuPont

Polystyrene, polystyrene copolymer, styrene acrylonitrile copolymer, acrylonitrile butadient styrene, polymethyl methacrylate, acrylic acid series copolymer, PEI such as ULTEM

(from the PEI of General Electric); Polyphenylene oxide is such as poly-(2,6-dimethyl phenylate) or polyphenyl ether/styrene blend such as NORYL 1000(from poly-(2,6-dimethyl phenylate) and the blend of polystyrene resin of General Electric); Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ester); Merlon such as LEXAN

(from the Merlon of General Electric); Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound; Or the mixture of any above-mentioned polymer. Blend can be by conventional machining technology preparation known in the art, for example melt blending or solution blending. In one embodiment, in polymer blend, there is not copolyesters. If use Merlon at the blend that is used for polymer blend of the present invention, then blend can be visually transparent. Yet, be used for polymer blend of the present invention and also consider to get rid of Merlon and comprise Merlon.

[0278] can be used for Merlon of the present invention can prepare according to known method, for example by making dihydroxy aromatic compounds and carbonate precursor such as phosgene, haloformate or carbonic ester ester, molecular weight regulator, acid acceptor and catalyst reaction. Be known in the art and for example be recorded among the USP 4,452,933 that for the preparation of the method for Merlon wherein the disclosure about the Merlon preparation is hereby incorporated by.

[0279] example of suitable carbonate precursor includes but not limited to carbonyl bromide, phosgene or its mixture; Diphenyl carbonate; Carbonic acid two (halogenophenyl) ester, such as carbonic acid two (trichlorophenyl) ester, carbonic acid two (tribromo phenyl) ester etc.; Carbonic acid two (alkyl phenyl) ester, for example carbonic acid two (tolyl) ester; Carbonic acid two (naphthyl) ester; Carbonic acid two (chloronaphthyl, methylnaphthyl) ester or its mixture; Bishaloformate with dihydroxy phenol.

[0280] example of suitable molecular weight regulator includes but not limited to phenol, cyclohexanol, methyl alcohol, alkylated phenol such as octyl phenol, p-t-butyl phenol etc. In one embodiment, molecular weight regulator is phenol or alkylated phenol.

[0281] acid acceptor can be the organic or inorganic acid acceptor. Suitable organic acid acceptor can be tertiary amine, and includes but not limited to the material such as pyridine, triethylamine, dimethylaniline, four butylamine etc. Examples of inorganic acceptors can be hydroxide, carbonate, bicarbonate or the phosphate of alkali metal or alkaline-earth metal.

[0282] operable catalyst includes but not limited to usually to help those of monomer and phosgene polymerization. Suitable catalyst includes but not limited to tertiary amine, for example triethylamine, tripropyl amine (TPA), N, N-dimethylaniline; Quaternary ammonium compound such as tetraethylammonium bromide, cetyltriethylammonium bromide, four n-heptyl ammonium iodides, four n-pro-pyl bromination ammoniums, tetramethyl ammonium chloride, TMAH, tetrabutylammonium iodide, benzyltrimethylammonium chloride; And quaternary phosphonium compound, for example normal-butyl three phenyl phosphonium bromides and first base three phenyl phosphonium bromides.

[0283] Merlon that can be used for polymer blend of the present invention can be copolyestercarbonates, such as USP 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484,4,465,820 and 4,981,898 put down in writing those, wherein each piece of these United States Patent (USP)s is hereby incorporated by about the disclosure of copolyestercarbonates.

[0284] being used for copolyestercarbonates of the present invention can be purchased and/or can be prepared by methods known in the art. For example, they can be typically by at least a dihydroxy aromatic compounds and phosgene and at least a diacid chloride, particularly m-phthaloyl chloride, paraphthaloyl chloride or both mixtures reaction acquisition.

[0285] in addition, comprise the polymer blend of polyester of the present invention and the common additives that blend polymer also can comprise polymer blend gross weight 0.01-25wt% or 0.01-20wt% or 0.01-15wt% or 0.01-10wt% or 0.01-5wt%, such as colorant, dyestuff, releasing agent, fire retardant, plasticizer, nucleator, stabilizing agent, include but not limited to UV stabilizing agent, heat stabilizer and/or its product, filler and impact modifying agent. Example well known in the art and that can be used for the commercially available impact modifying agent of typical case of the present invention includes but not limited to the ethylene/propene terpolymer; Functionalised polyolefin, as comprise those of methyl acrylate and/or glyceral methacrylate; The block copolymer impact modifying agent of styrene-based; With various acrylic acid series core/shell type impact modifying agents. For example, can be by the UV additive being added in the body or by applying hard conating or being introduced in the goods of manufacturing by coextrusion cover layer (cap layer). Also consider the residue of this additive part as polymer blend.

[0286] polyester of the present invention can comprise at least a chain extender.

[0287] suitable chain extender includes but not limited to multifunctional (including but not limited to difunctionality) isocyanates, and multi-functional epoxy's compound comprises for example epoxidization phenolic resin, and phenoxy resin. In certain embodiments, chain extender can add at the end of polymerization process or after polymerization process. If after polymerization process, add, then can or add and introduce chain extender by compounding during conversion process such as injection moulding or extrusion molding. The consumption of chain extender can change according to composition and the needed physical property of used concrete monomer, but is generally the about 10wt% of about 0.1wt%-, and the preferred about 5wt% of about 0.1wt%-is based on the gross weight of polyester.

[0288] reinforcing material can be used for the present composition. Reinforcing material can include but not limited to carbon filament, silicate, mica, clay, talcum, titanium dioxide, wollastonite, glass fragment, bead and fiber, and polymer fiber and combination thereof. In one embodiment, reinforcing material is glass, such as the fibrous glass silk, and the mixture of glass and talcum, glass and mica and glass and polymer fiber.

[0289] in another embodiment, the invention further relates to the manufacturing goods that comprise above-mentioned any polyester and blend.

[0290] in another embodiment, the invention further relates to the manufacturing goods that comprise any polyester described herein and blend. Extrusion molding, calendering and/or moulding article include but not limited to injection-molded item, extrudate, curtain coating extrudate, profile extrusion goods, melt-spun goods, thermoformed articles, extrusion molding mechanograph, injection blow molding mechanograph, injection stretch blow mechanograph, extrusion blow molded mechanograph and crowded base stretch-blow mechanograph. These goods can include but not limited to film, bottle (including but not limited to feeding bottle), container, thin plate and/or fiber.

[0291] polyester of the present invention and/or polyester blend compositions can be used to form fiber, film, mechanograph, container and thin plate. The method that polyester is formed fiber, film, mechanograph, container and thin plate is well known in the art. The example of potential mechanograph includes but not limited to: medical equipment such as dialysis machine, medical package, health treatment, commercial food product service product such as food disc, tumbler and depository dish, feeding bottle, food processing equipment, blender and mixing bowl, vessel, water bottle, fresh vegetables Freshness keeping disc, washer operation face and vacuum cleaner parts. Other potential mechanograph may include but not limited to glasses and framework. For example, this material can be used for preparing bottle, includes but not limited to feeding bottle, because it is transparent, tough and tensile, heat-resisting, and shows good hydrolytic stability.

[0292] in another embodiment, the invention further relates to and comprise the film that comprises polymer blend described herein and/or the manufacturing goods of thin plate.

[0293] being used for that film of the present invention and/or thin plate can have is apparent any thickness to those skilled in the art. In one embodiment, film of the present invention has the thickness that is not more than 40 mils. In one embodiment, film of the present invention has the thickness that is not more than 35 mils. In one embodiment, film of the present invention has the thickness that is not more than 30 mils. In one embodiment, film of the present invention has the thickness that is not more than 25 mils. In one embodiment, film of the present invention has the thickness that is not more than 20 mils.

[0294] in one embodiment, thin plate of the present invention has the thickness that is not less than 20 mils. In another embodiment, thin plate of the present invention has the thickness that is not less than 25 mils. In another embodiment, thin plate of the present invention has the thickness that is not less than 30 mils. In another embodiment, thin plate of the present invention has the thickness that is not less than 35 mils. In another embodiment, thin plate of the present invention has the thickness that is not less than 40 mils.

[0295] the invention further relates to film and/or the thin plate that comprises polymer blend of the present invention. The method that polyester is formed film and/or thin plate is well known in the art. The example of film of the present invention and/or thin plate includes but not limited to cast film and/or thin plate, calendered film and/or thin plate, compression molded films and/or thin plate, solution casting film and/or thin plate. The method for preparing film and/or thin plate includes but not limited to extrusion molding, calendering, compression moulding and solution casting.

[0296] example by the potential goods that can be used for the preparation of film of the present invention and/or thin plate includes but not limited to single axle drawn membrane, biaxially oriented film, shrinkable film (no matter being single shaft or biaxial stretch-formed), liquid crystal display film (including but not limited to diffusing panel, compensation film and protective film), thermoforming thin plate, Making Film, outdoor mark, skylight, coating, coated article, painting products, laminated material, laminated product and/or many walls film or thin plate.

[0297] " Making Film " used herein is the film that is printed with thermal curable printing ink (but for example heating curable printing ink or air curing printing ink) or radiation curable ink thereon or wherein. " curable " refers to carry out polymerization and/or crosslinked. Except printing ink, Making Film also can be chosen wantonly and comprise varnish, coating, laminated material and adhesive.

[0298] exemplary hot or air curing printing ink comprise the pigment that is dispersed in one or more standard vector resins. This pigment can be 4B toner (PR57), 2B toner (PR48), lake red C (PR53), lithol red (PR49), iron oxide (PR101), permanent bordeaux R (PR4), permanent bordeaux 2G (P05), pyrazolone orange (P013), diarylide yellow (PY12,13,14), monoazo yellow (PY3,5,98), phthalocyanine green (PG7), phthalocyanine blue, β type (PB15), dark blue (PB62), permanent violet (PV23), titanium dioxide (PW6), carbon black (stove/flue) (PB7), PMTA powder, green, blue, purple (PR81, PG1, PB1, PV3), copper ferrocyanide complex compound (PR169, PG45, PB62, PV27) etc. (symbol in the above-mentioned bracket refers to the general colour index by Britain dyer author association (the Society of Dyers and Colourists) formulation). This pigment and combination thereof can be used for obtaining shades of colour, include but not limited to white, black, blueness, purple, redness, green, yellow, cyan, magenta or orange.

[0299] other exemplary printing ink comprises that radiation curable ink is disclosed in USP 5,382, and in 292, wherein the disclosure of this printing ink is hereby incorporated by.

[0300] example that is used for the typical carriers resin of standard ink comprise have nitrocellulose, acid amides, carbamate, epoxides, acrylate and/or ester functional group those. The standard vector resin comprises one or more of nitrocellulose, polyamide, polyurethane, ethyl cellulose, cellulose-acetate propionate, (methyl) acrylate, polyvinyl butyral resin, polyvinyl acetate, polyvinyl chloride etc. This resin can with widely used blend (comprising nitrocellulose/polyamide and nitrocellulose/polyurethane) blend.

[0301] ink resin usually can solvation or dispersion in one or more solvents. Used typical solvent includes but not limited to water, alcohol (such as ethanol, 1-propyl alcohol, isopropyl alcohol etc.), acetic acid esters (for example n-propyl acetate), aliphatic hydrocarbon, aromatic hydrocarbon (for example toluene) and ketone. This solvent usually can be being enough to providing viscosity at least 15 seconds, and for example at least 20 seconds, at least 25 seconds, or the amount of the printing ink of 25-35 second mixes, and described viscosity is praised grace (Zahn) cup mensuration at #2 known in the art. In one embodiment, polyester has enough Tg values, obtaining hot formability, and allows easily to be printed onto on the Making Film.

[0302] in one embodiment, Making Film has at least a hot formability, toughness, the transparency, chemical resistance, Tg and the flexible performance of being selected from.

[0303] Making Film can be used for various application, for example in-die decoration production, embossing goods, hard coating article. Making Film can be smooth or veined.

[0304] exemplary Making Film includes but not limited to nameplate, membrane switch cap rock (for example being used for utensil); Point of sale displays; Plane or in-mold decoration plate on the washing machine; Plane touch pad on the refrigerator (for example capacitance touch pad array); Flat board on the baking oven; Automobile decoration trim panel (for example polyester laminate); Automobile instrument group plate; Phone cover; Heating and Ventilation Control display; The automobile control panel; The automobile gear variable speed plate; Control display device or the alarm signal of fascia; Facing on the home appliances, rotating disk or display; Facing on the washing machine, rotating disk or display; Facing on the dish-washing machine, rotating disk or display; The keyboard of electronic equipment; The keyboard of mobile phone, personal digital assistant's (PDAs or laptop computer) or remote controllers; The display of electronic equipment; The display of hand-held electric subset such as phone and PDAs; The panel and the shell that are used for mobile or standard telephone; Logo on the electronic equipment; Logo with mobile phone.

[0305] many walls film or thin plate refer to as the thin plate by a plurality of layers of section bar extrusion that forms that connect by vertical rib each other. The example of many walls film or thin plate includes but not limited to outdoor baffle (for example greenhouse and commercial shelter).

[0306] example that comprises the extrudate that can be used for polymer blend of the present invention includes but not limited to the thermoforming thin plate, be used for film, outdoor mark, skylight, the many walls film that Making Film uses, plastic sheeting and liquid crystal display (LCD) film that is used for the resin glass laminated material, includes but not limited to diffusing panel, compensation film and protective film for LCD.

[0307] within the scope of the present invention other goods that comprise polymer blend of the present invention include but not limited to safety/motion goods (such as including but not limited to safety screen, face shield, sports goggles [racquetball, skiing etc.], the anti-riot baffle plate of police); The corrugated sheet goods; Amusement/outdoor vehicle and equipment (example includes but not limited to meadow tractor, snowmoblie, motorcycle windshield, camping window, Caddy windshield, Wave Race); (example includes but not limited to diffusing globe, office, family and commercial fixture for dwelling house and commercial lighting equipment; High-intensity discharge (HID) lighting apparatus); Telecommunications/commerce/electronic equipment (example includes but not limited to phone housing, TV shell, computer casing, casing of sound equipment, PDAs etc.); Optical medium; The process hides bed; Multi-layered sheet, extruded product; The hard medical package; The intravenous assembly; Dialysis filter shell; The haemodialysis container; Sterilization container (for example Baby Care sterilization container); Comfort nipple, pad (example includes but not limited to screwdriver, hammer etc.); Thermoplastic article; Sound barrier; The outer part (front lamp cover, rear light cover, side window, sun proof) of automobile; Hard running stores/industrial packaging; Bathtub; Shower; Heat channel; The machine protector; The automatic vending machine display board; Instrument; Motion and recreational facilities (example: swimming pool fence, gymnasium seat, hockey field, open-air structure, T-bar lift); Crawl; The ophthalmic product; Ornamental barrier window; With automobile internals (instrument group plate).

[0308] the invention still further relates to bottle as herein described. The method that polyester is configured as bottle is well known in the art. The example of bottle includes but not limited to such as following bottle: medicine bottle; Feeding bottle; Water bottle; Juice bottle; The large scale commercial product water bottle of heavy 200-800 gram; Include but not limited to the beverage bottle of 2 litre flasks, 20 ounces of bottles, 16.9 ounces of bottles; Medical bottle; The use in personal care bottle; The carbonated soft drink bottle; Hot canned bottle; Water bottle; Alcoholic beverage bottles such as beer bottle and burgundy bottle; With the bottle that comprises at least one handle. These bottles include but not limited to injection blow molding bottle, injection stretch blow bottle, extrusion blow molded bottle and crowded base stretch blow bottle. The method for preparing bottle includes but not limited to extrusion blow molded, crowded base stretch-blow, injection blow molding and injection stretch blow. In each case, the invention further relates to preformed member (or parison) for the preparation of every kind of described bottle.

[0309] these bottles include but not limited to injection blow molding bottle, injection stretch blow bottle, extrusion blow molded bottle and crowded base stretch blow bottle. The method for preparing bottle includes but not limited to extrusion blow molded, crowded base stretch-blow, injection blow molding and injection stretch blow.

[0310] other example of container includes but not limited to the container for cosmetics and personal care applications, comprises bottle, jar, phial and pipe; Sterilization container; The buffet steamer; Food pan or dish; The frozen food dish; But microwave cooking food disc; The hot canning container; Amorphous lid or the thin plate of sealing or covering food disc; Food conservation container; For example, box; The large tank of flat glass, handlebar, teacup, bowl include but not limited to for those of the little vessel in dining room; Container for drink; The retort pouch food containers; Centrifuge bowl; Vacuum cleaner case and collection and treatment box.

[0311] " the little vessel in dining room " used herein refer to any container for edible or supplying food. The example of the little vessel in dining room includes the large tank, teacup of handle, the optional large cup (comprise and decorate large cup, list or the large cup of double-walled, the large cup that pressurizes, the large cup of vacuum) that comprises handle, bowl (for example serve the meals bowl, soup bowl, salad bowl) and plate (for example eat and supply service plate, such as informal dinner dish, plate, dinner plate).

[0312] in one embodiment, the container as the little vessel in dining room can bear the refrigerator temperature that is higher than 0 ℃ (for example 2 ℃)-5 ℃. In another embodiment, the little vessel container in dining room can bear steam treatment and/or commercial dish washer condition. In another embodiment, the little vessel container in dining room can bear microwave condition. In one embodiment, the little vessel container in dining room has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg, hydrolytic stability and dish-washing machine stability.

[0313] in one embodiment, the medical equipment that comprises polymer blend of the present invention includes but not limited to comprise the medical equipment of ultraviolet solidifiable coating based on siloxanes, at least a portion in surfaces of medical devices comprises the polyester that contains cyclobutanediol, it has improved anti-albumen and biocompatibility, can be applied on the various base materials, and overcome several difficulties of pointing out in the disclosed method in front.

[0314] in one embodiment, the present invention includes thermoplastic article, typically be the light sheet material form, wherein be embedded with decorative material, it comprises any composition as herein described.

[0315] " food conservation container " used herein is in the temperature that is generally used for storing with supplying food and beverage, for example between the depfreeze temperature to such as the temperature in low-temperature bake oven or be used for the hot temperature of the temperature of hot beverage distributor, can store and/or supply heat and/or ice confectionery and/or beverage. In one embodiment, food conservation container can be sealed to reduce Food Oxidation speed. In another embodiment, food conservation container can be used to the client of dining to show and supplying food. In one embodiment, food conservation container can be stored in the household freezer, for example in the temperature that is lower than 0 ℃, such as-20 to 0 ℃ temperature (for example-18 ℃). In another embodiment, food conservation container can be higher than 0 ℃ (for example 2 ℃) foodstuff storing in 5 ℃ the refrigerator. In another embodiment, food conservation container can bear steam treatment and/or commercial dish washer condition. In another embodiment, food conservation container can bear microwave condition.

[0316] example of food conservation container comprises buffet steamer, dining room steam disc, food pan, hot and cold beverage dispenser (for example refrigerator beverage dispenser, automatic heating or cold drink distributor) and food storage case.

[0317] in one embodiment, food conservation container has at least a additional properties that are selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0318] in one embodiment of the invention, thermoplastic articles is provided, it is by to one or more laminated materials or " sandwich " applies heat and pressure obtains, wherein at least a described laminated material comprises (1) at least one deck top sheet material in order, (2) one deck ornament materials at least, and (3) one deck bottom thin plate material at least. Randomly, adhesive phase can use between (1) and (2) and/or between (2) and (3). The layer (1) of this " sandwich ", any one deck of (2) and/or (3) can comprise any composition of the present invention.

[0319] " ophthalmic product " used herein refers to according to the single eyeglass lens of making of optometry, non-according to eyeglass lens, sunglass lens and the glasses of the single system of optometry and the framework of sunglasses.

[0320] in one embodiment, the ophthalmic product is selected from band look eyeglass lens and hard conating eyeglass lens. In one embodiment, eyeglass lens such as band look eyeglass lens or hard conating eyeglass lens, comprises at least a polarizing coating or polarization additive.

[0321] in one embodiment, when product was lens, the ophthalmic product had 1.54 to 1.56 refractive index.

[0322] in one embodiment, the ophthalmic product can have at least a performance that is selected from toughness, the transparency, chemical resistance (such as bearing lens cleaning agent, oil, hair product etc.), Tg and hydrolytic stability.

[0323] " outdoor mark " used herein refers to the surface that formed by polyester as herein described, or contains symbol (such as numeral, letter, word, figure etc.), pattern or the design that scribbles polyester as herein described or polyester film. In one embodiment, outdoor mark comprises Printing Marks, pattern or the design that contains polyester. In one embodiment, this mark can bear typical weather conditions, like rain, snow, ice, rain and snow mixed, high humility, heat, wind, sunlight or their combination, reaches the time enough section, for example one day to several years or longer time.

[0324] exemplary outdoor mark includes but not limited to billboard, neon sign, electric-field luminescent mark, electric mark, fluorescence labeling and light emitting diode (LED) display. The mark of the mark that other exemplary indicia includes but not limited to paint, mark that vinylite is decorated, thermoforming and the mark of hard conating is arranged.

[0325] in one embodiment, outdoor mark has at least a performance that is selected from hot formability, toughness, the transparency, chemical resistance and Tg.

[0326] " automatic vending machine display board " used herein refers to panel or the side plate on automatic vending machine, and it allows the consumer to observe article for sale, or about the advertisement of these article. In one embodiment, the automatic vending machine display board can be the visually transparent plate of automatic vending machine, and the consumer sees through it and observes article for sale. In other embodiments, the automatic vending machine display board can have enough rigidity in order to content is contained in this machine and/or stops destruction and/or helmet to be stolen.

[0327] in one embodiment, the automatic vending machine display board can have size commonly known in the art, such as the flat type display panels in snack, beverage, puffed rice or adhesive sticker paster/ticket automatic vending machine, and the capsule-type display board in for example Gum-making process machine or bulk candy processing machine.

[0328] in one embodiment, the automatic vending machine display board can be chosen wantonly and contain advertising media or qualified products sign. This type of information can by method well known in the art for example silk screen printing apply.

[0329] in one embodiment, the automatic vending machine display board can anti--100 ℃ to 120 ℃ temperature. In another embodiment, the automatic vending machine display board can become anti-UV's by being added on for example at least a UV additive disclosed herein.

[0330] in one embodiment, the automatic vending machine display board has at least a performance that is selected from hot formability, toughness, the transparency, chemical resistance and Tg.

[0331] " point of sale displays " used herein refers to have the visually all or part of casing that surrounds of transparent panel that at least one is used for showing article. Point of sale displays usually is used for retail shop to attract client's sight. Exemplary sales point display comprises the box of the showing stand, counter top, the placard pallet that surrounds, display box (for example prize display box), mark framework and computer disc such as CD and the DVD that surround wall. Point of sale displays can comprise shelf and additional container, such as the clamper of magazine or brochure. Those of ordinary skills can easily be contemplated to the shape and size of the point of sale displays of determining according to the article of showing. For example, this display may diminish to the box of jewelry, or shows the larger cupboard that surrounds of many prizes.

[0332] in one embodiment, point of sale displays has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0333] " intravenous assembly " used herein refers to from the assembly that is used for fluid (for example medicine, nutrients) is administered to patient's blood flow of polymeric material manufacturing. In one embodiment, the intravenous assembly is stiff member.

[0334] exemplary intravenous assembly comprises y position (y-site) connector assembly, Rule (luer) assembly, filter, plug valve, manifold and valve. Y-position connector has " Y " shape, comprise the first branch with first passage, the second branch with second channel and be communicated with described the first and second branches and have the 3rd branch with the third channel of described the first and second channel connections. Rule assembly comprises Luer lock, connector and valve.

[0335] in one embodiment, the intravenous assembly can bear sterilization treatment, such as high pressure steam sterilization, eo sterilization, radiation sterilization and hot air sterilization. In one embodiment, the intravenous assembly has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0336] " dialysis filter shell " used herein refers to have the protecting sheathing of a plurality of openings, and this opening is used for holding many doughnuts or tubing, and it can be used for dialysate is introduced and discharged in the patient body. In one embodiment, the cross-sectional area of an opening is 0.001cm in protecting sheathing²-be lower than 50cm²。

[0337] in one embodiment, dialysis filter shell has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0338] " haemodialysis container " used herein refers to for those containers to patient's input and output blood. Exemplary haemodialysis container comprises oxygenator, box, centrifuge bowl, collection and process tank, pump barrel body, porta venarum shell and dialyzer shell. Oxygenator can be removed carbon dioxide from patient's venous blood, oxygen is incorporated into make it to change into arterial blood in the blood of extracting out, then in the blood input patient body with oxygenation. Other container can be used in and temporarily holds the blood that institute extracts out or stores, and inputs in the patient body afterwards.

[0339] in one embodiment, the haemodialysis container can bear sterilization treatment, such as high pressure steam sterilization, eo sterilization, radiation sterilization and hot air sterilization. In one embodiment, the haemodialysis container has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0340] " device component " used herein refers to the hard parts used with utensil. In one embodiment, this device component can partially or even wholly be dismantled from utensil. In another embodiment, this device component is typically from the parts of polymers manufacturing. In one embodiment, this device component visually is transparent.

[0341] exemplary device component comprises those parts that need toughness and durability, such as the employed cup of food processing equipment, blender, blender and chopper and bowl; Can bear refrigerator and household freezer temperature (for example from greater than 0 ℃ (for example 2 ℃) to 5 ℃ refrigerator temperatures, or the household freezer temperature, for example be lower than 0 ℃ temperature, such as-20 ℃ to 0 ℃ temperature, parts for example-18 ℃) are such as refrigerator and household freezer plate, cupboard and shelf; The parts that have enough hydrolytic stabilities under up to 90 ℃ temperature are such as washing gate, steam cleaner tank, teapot and coffee pot; With vacuum cleaner tank and dirt cup.

[0342] in one embodiment, these device components have at least a performance that is selected from toughness, the transparency, chemical resistance, Tg, hydrolytic stability and dish-washing machine stability. Device component also can be selected from the steam cleaner tank, and the latter can have at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability in one embodiment.

[0343] in one embodiment, the polyester that can be used for device component has Tg and this device component of 105-140 ℃ and is selected from vacuum cleaner tank and dirt cup. In another embodiment, the polyester that can be used for device component has Tg and this device component of 120-150 ℃ and is selected from steam cleaner tank, teapot and coffee pot.

[0344] " skylight " used herein refers to be fixed to the plate of the Tou Guoed light on the roof surface, so that this plate consists of the part of ceiling. In one embodiment, this plate is rigidity, for example has the size that is enough to realize stability and durability, and this size can easily be determined by those skilled in the art. In one embodiment, this skylight board has the thickness greater than 3/16 inch, such as at least 1/2 inch thickness.

[0345] in one embodiment, this skylight board visually is transparent. In one embodiment, this skylight board can see through at least 35% visible light, and at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, this skylight board comprises at least a UV additive, and the latter allows skylight board blocking-up at the most 80%, 90%, or 95% UV light at the most.

[0346] in one embodiment, this skylight has at least a performance that is selected from hot formability, toughness, the transparency, chemical resistance and Tg.

[0347] " outdoor baffle " used herein structure of referring to have the roof of at least one rigid plate and/or wall being arranged, it can be to providing at least some protections such as sunshine, rain, snow, wind, the factor such as cold. In one embodiment, this open air baffle has at least roof and/or one or more wall. In one embodiment, outdoor baffle has the size that is enough to realize stability and durability, and this size can easily be determined by those skilled in the art. In one embodiment, this open air baffle plate has the thickness greater than 3/16 inch.

[0348] in one embodiment, outdoor shield visually is transparent. In one embodiment, this open air shield can see through at least 35% visible light, and at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, this open air shield comprises at least a UV additive, and the latter allows outdoor baffle blocking-up at the most 80%, 90%, or 95% UV light at the most.

[0349] exemplary outdoor baffle comprises security windowpane, transportation baffle (for example bus baffle), telephone booth and smoking baffle. In one embodiment, wherein baffle is transportation baffle, telephone booth or smoking baffle, and this baffle has at least a performance that is selected from hot formability, toughness, the transparency, chemical resistance and Tg. In one embodiment, wherein baffle is the security windowpane, and this baffle has at least a performance that is selected from toughness, the transparency, chemical resistance and Tg.

[0350] " canopy " used herein refer to can be to providing the roof structure of at least some protections such as sunshine, rain, snow, wind, the factor such as cold. In one embodiment, this roof structure comprises at least one rigid plate whole or in part, for example has the size that is enough to realize stability and durability, and this size can easily be determined by those skilled in the art. In one embodiment, this canopy plate has the thickness greater than 3/16 inch, such as at least 1/2 inch thickness.

[0351] in one embodiment, the canopy plate visually is transparent. In one embodiment, this canopy plate can see through at least 35% visible light, and at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, this canopy plate comprises at least a UV additive, and the latter allows canopy blocking-up at the most 80%, 90%, or 95% UV light at the most.

[0352] exemplary canopy comprises aisle, roof light units, glass sunlight house, aircraft canopy and the awning of covering. In one embodiment, this canopy has at least a toughness, the transparency, chemical resistance, Tg and the flexible performance of being selected from.

[0353] " sound barrier " used herein refer to when with two points of the same distance that does not have sound barrier between sound transmission when comparing, the rigid structure of the sound transmission amount of another point on can reducing from a point on the side of structure to opposite side. Reducing the validity of sound transmission can analyze by method well known in the prior art. In one embodiment, the amount of the sound transmission of minimizing is 25% to 90%.

[0354] in another embodiment, this sound barrier can be used as transaudient grade point and grades, as at for example ASTM E90, " Standard Test Method for Laboratory Measurement of Airborne Sound Transmission Loss of Building Partitions and Elements ", with ASTM E413, described in " Classification of Rating Sound Insulation ". STC 55 sound barriers can reduce to 60dBA with the sound～130dBA of jet engine, and it is sound level in the typical office. Noiseless room can have the sound level of 0-20dBA. Those of ordinary skills can build and arrange this sound barrier to realize required STC sound level grade. In one embodiment, this sound barrier has at least 20 STC sound level, the sound level such as 20 to 60.

[0355] in one embodiment, this sound barrier comprises that a plurality of plates that connect and arrange are to realize desirable acoustical ratings. This sound barrier can be along street and Highway house in order to the car noise of decaying. Additionally, this sound barrier can be used for family or office, as discrete plate, or is inserted in the building structure inside of wall, floor, ceiling, door and/or window.

[0356] in one embodiment, this sound barrier visually is transparent. In one embodiment, this sound barrier can see through at least 35% visible light, and at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, this sound barrier comprises at least a UV additive, and the latter allows sound barrier blocking-up at the most 80%, 90%, or 95% UV light at the most.

[0357] in one embodiment, this sound barrier has at least a performance that is selected from toughness, the transparency, chemical resistance and Tg.

[0358] " greenhouse " used herein refers to the structure of surrounding for the cultivation of plant and/or protection. In one embodiment, the greenhouse can be maintained cultivate plants needed humidity and/or gas (oxygen, carbon dioxide, nitrogen etc.) content, simultaneously can be to providing at least some protections such as sunshine, rain, snow, wind, the factor such as cold. In one embodiment, the roof in greenhouse comprises at least one rigid plate whole or in part, for example has the size that is enough to realize stability and durability, and this size can easily be determined by those skilled in the art. In one embodiment, greenhouse panels has the thickness greater than 3/16 inch, such as at least 1/2 inch thickness.

[0359] in one embodiment, greenhouse panels visually is transparent. In another embodiment, basically all roofs in greenhouse and wall visually are transparent. In one embodiment, this greenhouse panels can see through at least 35% visible light, and at least 50%, at least 75%, at least 80%, at least 90%, or even at least 95% visible light. In another embodiment, this greenhouse panels comprises at least a UV additive, and the latter allows greenhouse panels blocking-up at the most 80%, 90%, or 95% UV light at the most.

[0360] in one embodiment, this greenhouse panels has at least a performance that is selected from toughness, the transparency, chemical resistance and Tg.

[0361] " optical medium " used herein refers to information storage medium, and wherein information exchange is crossed the employing bombardment with laser beams and come imprinting, the light in visible wavelength region for example, as have 600nm to the light of the wavelength of 700 nm. By the radiation of laser beam, the irradiation zone that is subjected to of imprinting layer is changed its physics or chemical characteristic by heating partly, and the imprinting layer be subjected to form concave point in the irradiation zone. Because the optical characteristics of formed concave point is different from not by the optical characteristics in the zone of radiation, this digital information is got off with the optical mode imprinting. This imprinting information can read by playback program, this program generally comprises following steps: adopt this imprinting layer of bombardment with laser beams that has with at the used identical wavelength of laser beam of imprinting program, and the light reflection difference that detects between concave point and their periphery is different.

[0362] in one embodiment, the optical medium imprinting dye coating and the reflection layer that comprise transparent disc with spirality prefabricated groove, be arranged in prefabricated groove in (by adopting bombardment with laser beams imprinting information thereon). Optical medium is optional can be by consumer's imprinting. In one embodiment, optical medium is selected from compact disk (CD) and digital video disc (DVD). Optical medium can sold after the in advance imprinting information, but or as the sale of imprinting dish.

[0363] in one embodiment, the following at least a polyester of the present invention that comprises: at least one protective layer of base material, optical medium and the imprinting layer of optical medium.

[0364] in one embodiment, optical medium has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0365] " Baby Care sterilization container " used herein refers to that this container is used for the family expenses sterilization of infant care product through constructing to hold the container of infant care product. In one embodiment, the Baby Care sterilization container is the infant bottle sterilization container.

[0366] in one embodiment, the Baby Care sterilization container has at least a additional properties that are selected from toughness, the transparency, chemical resistance, Tg, hydrolytic stability and dish-washing machine stability.

[0367] " comforting nipple " used herein comprises the pliability nipple that surrounded by rigidity mouth shield (for example be used for baby sucking and/or sting), wherein rigidity mouth shield randomly is connected to a handle, allow baby or monitoring adult have one easily structure catch and/or hold and comfort nipple. This handle can be rigidity or flexible.

[0368] in one embodiment, comforting nipple can be made by various ingredients. For example, nipple can pass at the center of mouth shield a hole. Handle can or can integrally not be connected on mouthful shield. Handle can be rigidity or flexible.

Nipple and a mouthful shield of [0369] in another embodiment, comforting nipple are shaped as integral unit. Generally, the selection of plastics is by the control that needs that provides than mouth shield and the handle of rigidity. In this embodiment, the nipple of comforting nipple can be more rigid, but still is baby sucking or stings desirable.

[0370] in one embodiment, comfort nipple and have at least a performance that is selected from toughness, the transparency, chemical resistance, Tg, hydrolytic stability and dish-washing machine stability.

[0371] " retort pouch food containers " used herein refers to flexible receptacle or the pouch for storage food and/or beverage, and wherein food and/or beverage are sealed to carry out the long-term storage of not putting into refrigerator. This food can be sealed under vacuum or inert gas. The retort pouch food containers can comprise at least one polyester layer, for example the single or multiple lift container. In one embodiment, laminated vessel comprises light reflection internal layer, for example metallized film.

[0372] in one embodiment, at least a food that is selected from plant, fruit, cereal, soup, meat, meat products, dairy products, soy sauce, flavouring and baked goods is loaded in the retort pouch food containers.

[0373] in one embodiment, the retort pouch food containers has at least a performance that is selected from toughness, the transparency, chemical resistance, Tg and hydrolytic stability.

[0374] " glass laminates " used herein refers to that wherein one deck coating comprises described polyester at least at least one deck coating on glass. Coating can be film or thin plate. Glass can be transparent, colored or reflexive. In one embodiment, laminated material for good and all is bonded on glass, for example in heating with add and depress the glass product of using this laminated material and forming single solid lamination. The one or both sides of glass can lamination. In certain embodiments, glass laminates contains the coating that comprises polymer blend of the present invention more than. In other embodiments, glass laminates comprises a plurality of glass substrates, and more than one the coating that comprises polymer blend of the present invention.

[0375] the exemplary glass laminated material comprises windowpane (windowpane that for example is used for skyscraper, building entrance), safety glass, the windshield, bulletproof glass or the bullet-resistant glass that are used for transport applications (for example automobile, bus, jet plane, armored vehicle), fiber glass (for example being used for bank), anti-hurricane glass or anti-hurricane glass, aircraft cabin window, mirror, daylight glass plate, flat-panel monitor and implosion guard window. Glass laminates can be visually transparent, frosted, etched or embossing.

[0376] in one embodiment, glass laminates can tolerate-100 to 120 ℃ temperature. In another embodiment, by adding for example at least a UV additive, as disclosed herein, glass laminates can be anti-UV.

[0377] film of the present invention and/or thin plate layer being pressed onto method on glass is known to those skilled in the art. Do not use the lamination of adhesive phase to be undertaken by vacuum lamination. In order to obtain the effective adhesive that has between glassy layer and the laminated material, in one embodiment, glass has low surface roughness.

[0378] selectively, but the two-sided tape, adhesive phase or the gelatin layer that obtain by the adhesive of using for example hot melt, contact adhesive or heat sensitive adhesive or UV or electronic beam curing can be used for being bonded to laminated material of the present invention on glass. Adhesive phase can the paint glass plate, on laminated material or both, and can be protected by peel ply, and this peel ply can will removed before the lamination.

[0379] in one embodiment, glass laminates has at least a performance that is selected from toughness, the transparency, chemical resistance, hydrolytic stability and Tg.

[0380] abbreviation used herein " wt " expression " weight ".

[0381] the following example further illustrates the composition that can how prepare and estimate theme of the present invention, and wishes it is that of the present invention illustrating do not wished to limit its scope purely.Except as otherwise noted, part be weight part, temperature is degree centigrade or is in room temperature, and pressure is or near normal atmosphere.

Embodiment

[0382] the following example illustrates prevailingly and how to prepare polyester, and with comprise 1,4 cyclohexane dimethanol and/or glycol residue, but lack 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol is compared, use 2,2,4,4-tetramethyl--1,3-cyclobutanediol (with various cis/trans mixtures) is to the influence of various polyester performances such as toughness, second-order transition temperature, logarithmic viscosity number etc.In addition, based on the following example, it will be understood by those skilled in the art that how thermo-stabilizer of the present invention can be used for containing the preparation of the polyester of this thermo-stabilizer.

Testing method

[0383] logarithmic viscosity number of polyester be in 60/40 (wt/wt) phenol/tetrachloroethane with the concentration of 0.25g/50ml 25 ℃ of mensuration, and with the dL/g record.

[0384] except as otherwise noted, second-order transition temperature (Tg) is TA DSC 2920 instruments that use Thermal Analyst Instruments according to ASTM D3418 with the scan rate measurement of 20 ℃/min.

[0385] glycol content of composition and cis/trans ratios are by proton magnetic resonance (PMR) (NMR) spectral measurement.All NMR spectrums are recorded on the JEOL Eclipse Plus 600MHz nuclear magnetic resonance spectrometer, use chloroform-trifluoroacetic acid (70-30 volume/volume) for polymkeric substance, perhaps use 60/40 (wt/wt) phenol/tetrachloroethane that has added deuterochloroform to be used for the lock field for the oligopolymer sample.By contrasting 2,2,4,4-tetramethyl--1, the model list of 3-cyclobutanediol-and dibenzoate carry out 2,2,4,4-tetramethyl--1, the peak of 3-cyclobutanediol resonance is pointed out.These model compounds are near the resonant position of finding in polymkeric substance and oligopolymer.

[0386] hypocrystalline time t _1/2Be to determine over time by the transmittance of measuring sample on the temperature controlled hot platform by laser apparatus and photoelectric detector.This measurement is by being exposed to temperature T with polymkeric substance _MaxAnd subsequently it is cooled to desired temperatures and carries out.By hot platform sample is remained on desired temperatures subsequently, measure transmissivity simultaneously over time.At first, sample is visually transparent, has high transmission rate, and becomes opaque along with the sample crystallization.The hypocrystalline time record is that transmittance is the time of a half between initial transmittance and the final transmittance.T _MaxBe defined as the required temperature of fusing sample crystal region (if having crystal region).The T that reports in following examples _MaxRepresentative was heated every kind of sample to nurse one's health the temperature of this sample before the hypocrystalline time measurement.T _MaxTemperature depends on to be formed and generally is different for every kind of polyester.For example, PCT can be heated to above certain temperature of 290 ℃ with the fusion-crystallization zone.

[0387] density is to use the gradient column density 23 ℃ of mensuration.

[0388] melt viscosity of report is measured by using Rheometrics DynamicAnalyzer (RDA II) herein.In the temperature of being reported with the variation of the frequency measurement melt viscosity of 1-400rad/sec with shearing rate.Zero shears melt viscosity (η ₀) be by the estimated melt viscosity of data of under zero shearing rate, extrapolating with methods known in the art.This step is automatically performed by Rheometrics Dynamic Analyzer (RDA II) software.

[0389] polymkeric substance 80-100 ℃ in vacuum drying oven dry 24 hours, and injection moulding on the B0y22S mould machine obtains 1/8 * 1/2 * 5 inches deflection band samples.According to ASTM D256 these band samples being cut into length is 2.5 inches and along 1/2 inch die-cut 10 mil breach that obtain of width.Determine 23 ℃ average izod impact strength by measuring 5 samples.

[0390] in addition, use 5 samples of 5 ℃ of incremental testings to determine the brittle-ductile transition temperature in differing temps.Temperature when the brittle-ductile transition temperature is defined as the fragility mode that 50% samples met represented by ASTM D256.

[0391] colour of report is to adopt Hunter Lab Ultrascan XESpectrophotometer (Hunter Associates Laboratory Inc. herein, Reston, VA) measuring method is with the CIELAB L of following parameters according to ASTM D 6290-98 and ASTM E308-99 measurement ^*, a ^*And b ^*Value: (1) D65 twinkler, (2) 10 degree viewers, (3) comprise the reflective-mode of specular angle, (4) big area is watched, and (5) 1 " mouthful size.This measuring method is can be undertaken by the polymer beads of 6mm screen cloth for grinding.

[0392] the % foam in polyester of the present invention is following measurement.Will be by MicroLiterAnalytical Supplies, Suwanee, the 20mL headspace phial of Ga. supply is placed on the balance of laboratory, adds the dry polymer of 5 grams and writes down weight.Add water then carefully, fill up, write down this weight then until phial.Record weight differential (wt1) also is used to assess the phial volume that does not contain the foamy polymkeric substance is housed.This numerical value is used for whole subsequent experimental.For each test, the 5 dry polymer samples that restrain are added in the clean headspace phial.The barrier film lid is contained in the top of phial, and this phial is with dried nitrogen purging about 1 minute then.Take off scavenging line, and the dried nitrogen pipeline that bubbler will be housed inserts in the barrier film lid to guarantee to keep the rare gas element of normal pressure (environmental stress) in phial in heat-up time.Then phial is put into the heating module (block) (boring cooperates closely so that phial is loosening) of 300 ℃ of preheatings and in this module, kept 15 minutes.This phial is removed then, air cooling on testing table.After the phial cooling, the phial top is removed, and is positioned on the balance of laboratory phial and weighing.In case the weight of noting is added water carefully fully to fill up this phial.Here, fully fill up this phial and be meant the top that adds water to phial, by with when measuring wt1) time equal height judge, and write down this weight.Calculate the difference (wt2) of these weight.By from wt1, deducting wt2, determine to be aggregated the amount (wt3=wt1-wt2) of " drainage water " that the foaming of thing causes.Suppose to test for this, the density of water is 1, and this allows these weight to be converted into volume, V1=wt1, V2=wt2, and V3=wt3." the % foam in polyester " calculates by following formula: density (the g/mL)+V3 of " the % foam in polymkeric substance "=V3/[(5g polymkeric substance/dry polyester].In this formula, comprise about 45mol%2,2,4,4-tetramethyl--1, the density of the dry polyester of the present invention of 3-cyclobutanediol is 1.17g/mL.The polyester that this 1.17g/mL value is tested for the composition that adopts in the 40%-50%mol TMCD scope does not have noticeable change.The density value of the dry polyester of about 20mol%TCMD is 1.18g/mL.The % foam is the volume % of the void volume in test post polymerization thing.Also can be determined at the vision grade of the afterwards final polymer samples of heating and cooling.

[0393] amount of the tin (Sn) among the embodiment is with the metal report of per 1,000,000 parts umber (ppm) and by using PANanalytical Axios senior wavelength dispersion x X-ray fluorescent spectrometer (Advanced wavelength dispersive x-ray fluorescence spectrometer) to be measured by x ray fluorescence (xrf) below.The amount of phosphorus is reported as the element phosphor of ppm similarly and also measures by the xrf that uses same instruments.

[0394] the 10-mil films of selected polyester sample is carried out compression moulding by using the Carver press at 240 ℃.As mentioned above for these measured thin film logarithmic viscosity numbers.

[0395] unless otherwise indicated, the cis/trans ratios that is used for the 1,4 cyclohexane dimethanol of following examples is about 30/70, and can be 35/65-25/75.Unless otherwise indicated, be used for 2,2,4 of following examples, 4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol is about 50/50.

[0396] following abbreviation is applicable to whole work embodiment and accompanying drawing.

TPA	Terephthalic acid
TPA	Terephthalic acid	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl--1,3-cyclobutanediol	DMT	Dimethyl terephthalate (DMT)
TMCD	2,2,4,4-tetramethyl--1,3-cyclobutanediol	CHDM	Cyclohexanedimethanol
IV	Logarithmic viscosity number	CHDM	Cyclohexanedimethanol
IV	Logarithmic viscosity number	TPP	Triphenyl phosphate
DBTO	Dibutyltin oxide	TPP	Triphenyl phosphate
DBTO	Dibutyltin oxide	DMTO	Cacodyl oxide base tin
η ₀	Zero shears melt viscosity	DMTO	Cacodyl oxide base tin
η ₀	Zero shears melt viscosity	T _g	Second-order transition temperature
T _bd	The brittle-ductile transition temperature	T _g	Second-order transition temperature
T _bd	The brittle-ductile transition temperature	T _max	The conditioning temperature of hypocrystalline time measurement

Embodiment 1

[0397] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol is more effective than ethylene glycol or m-phthalic acid aspect the crystallization rate that reduces PCT.In addition, present embodiment illustrates 2,2,4,4-tetramethyl--1, the benefit of 3-cyclobutanediol aspect second-order transition temperature and density.

[0398] the multiple following copolyesters of preparation.These copolyesters all adopt the 200ppm dibutyltin oxide as Preparation of Catalyst, with minimum catalyst type and concentration to Study on Crystallization during the influence of nucleogenesis.The cis/trans ratios of cyclohexanedimethanol is 31/69, and 2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol is recorded in the table 1.

[0399] for present embodiment, each sample has enough similar logarithmic viscosity number, gets rid of it effectively as variable thus in crystallization rate is measured.

[0400] is the hypocrystalline time of increment measurement melt with 10 ℃ and is recorded in the table 1 at 140-200 ℃.Get the fastest hypocrystalline time of every kind of sample as the minimum value of temperature variant hypocrystalline time, generally occur in 170-180 ℃.The fastest hypocrystalline time of sample is plotted among Fig. 1 as the function to the mol% of the comonomer of PCT modification.

[0401] data presentation, 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is more effective than ethylene glycol and m-phthalic acid aspect reduction crystallization rate (promptly improving the hypocrystalline time).In addition, 2,2,4,4-tetramethyl--1,3-cyclobutanediol have improved Tg and have reduced density.

Table 1

The hypocrystalline time (min)

Embodiment	Comonomer (mol%) ¹	IV (dl/g)	Density (g/ml)	T _g (℃)	T _max (℃)	140℃ (min)	150℃ (min)	160℃ (min)	170℃ (min)	180℃ (min)	190℃ (min)	200℃ (min)
Embodiment	Comonomer (mol%) ¹	IV (dl/g)	Density (g/ml)	T _g (℃)	T _max (℃)	140℃ (min)	150℃ (min)	160℃ (min)	170℃ (min)	180℃ (min)	190℃ (min)	200℃ (min)	1A	20.2％A ²	0.630	1.198	87.5	290	2.7	2.1	1.3	1.2	0.9	1.1	1.5
1B	19.8％B	0.713	1.219	87.7	290	2.3	2.5	1.7	1.4	1.3	1.4	1.7	1A	20.2％A ²	0.630	1.198	87.5	290	2.7	2.1	1.3	1.2	0.9	1.1	1.5
1B	19.8％B	0.713	1.219	87.7	290	2.3	2.5	1.7	1.4	1.3	1.4	1.7	1C	20.0％C	0.731	1.188	100.5	290	＞180	＞60	35.0	23.3	21.7	23.3	25.2
1D	40.2％A ²	0.674	1.198	81.2	260	18.7	20.0	21.3	25.0	34.0	59.9	96.1	1C	20.0％C	0.731	1.188	100.5	290	＞180	＞60	35.0	23.3	21.7	23.3	25.2
1D	40.2％A ²	0.674	1.198	81.2	260	18.7	20.0	21.3	25.0	34.0	59.9	96.1	1E	34.5％B	0.644	1.234	82.1	260	8.5	8.2	7.3	7.3	8.3	10.0	11.4
1F	40.1％C	0.653	1.172	122.0	260	＞10 days	＞5 days	＞5 days	19204	＞5 days	＞5 days	＞5 days	1E	34.5％B	0.644	1.234	82.1	260	8.5	8.2	7.3	7.3	8.3	10.0	11.4
1F	40.1％C	0.653	1.172	122.0	260	＞10 days	＞5 days	＞5 days	19204	＞5 days	＞5 days	＞5 days	1G	14.3％D	0.646 ³	1.188	103.0	290	550	288	11.6	6.8	4.8	5.0	5.5
1H	15.0％E	0.728 ⁴	1.189	99.0	290	25.4	17.1	8.1	5.9	4.3	27	5.1	1G	14.3％D	0.646 ³	1.188	103.0	290	550	288	11.6	6.8	4.8	5.0	5.5

The remainder of the diol component of polyester is a cyclohexanedimethanol in 1 table 1; And the dicarboxylic acid component's of polyester remainder is a dimethyl terephthalate (DMT) in the table 1; If do not describe dicarboxylic acid, then it is the 100mol% dimethyl terephthalate (DMT).

2 100mol% cyclohexanedimethanols.

3 240 ℃ of grinding polyester press membrane by embodiment 1G.The gained film has the logarithmic viscosity number value of 0.575dL/g.

4 240 ℃ of grinding polyester press membrane by embodiment 1H.The gained film has the logarithmic viscosity number value of 0.652dL/g.

Wherein:

A is a m-phthalic acid

B is an ethylene glycol

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (about 50/50 cis/trans)

D is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (98/2 cis/trans)

E is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (5/95 cis/trans)

[0402] as table 1 and shown in Figure 1, improving the hypocrystalline time, promptly polymkeric substance reaches half required time aspect of its maximum degree of crystallinity, and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are than other comonomer, and be more effective as ethylene glycol and m-phthalic acid.By the crystallization rate (improving the hypocrystalline time) that reduces PCT, can be by the methods known in the art manufacturing based on as herein described 2,2,4,4-tetramethyl--1, the amorphous goods of the PCT of 3-cyclobutanediol modification.As shown in table 1, these materials can show than higher second-order transition temperature of other modification PCT copolyesters and lower density.

[0403] preparation of the polyester shown in the table 1 is described below.

Embodiment 1A

[0404] present embodiment illustrates the preparation that target group becomes the copolyesters of 80mol% dimethyl terephthalate (DMT) residue, 20mol% dimethyl isophthalate residue and 100mol% cyclohexanedimethanol residue (28/72 cis/trans).

[0405] mixture with 56.63g dimethyl terephthalate (DMT), 55.2g cyclohexanedimethanol, 14.16g dimethyl isophthalate and 0.0419g dibutyltin oxide places 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum then gradually and press in flask and reach 100mmHg in ensuing 5 minutes.Again that the flask internal drop is low to 0.3mmHg in ensuing 5 minutes.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.5 ℃, and logarithmic viscosity number is 0.63dl/g.NMR analysis revealed polymkeric substance comprises 100mol% cyclohexanedimethanol residue and 20.2mol% dimethyl isophthalate residue.

Embodiment 1B

[0406] present embodiment illustrates the preparation that target group becomes the copolyesters of 100mol% dimethyl terephthalate (DMT) residue, 20mol% glycol residue and 80mol% cyclohexanedimethanol residue (32/68 cis/trans).

[0407] mixture with 77.68g dimethyl terephthalate (DMT), 50.77g cyclohexanedimethanol, 27.81g ethylene glycol and 0.0433g dibutyltin oxide places 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and arrived up to 280 ℃ at 30 minutes internal heating subsequently at 210 ℃.In case reach 280 ℃, in ensuing 5 minutes, apply vacuum gradually and in flask, press and reach 100mmHg.Again that the flask internal drop is low to 0.3mmHg in ensuing 10 minutes.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 87.7 ℃, and logarithmic viscosity number is 0.71dl/g.NMR analysis revealed polymkeric substance comprises the 19.8mol% glycol residue.

Embodiment 1C

[0408] present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 20mol%2, and 2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue and 80mol% cyclohexanedimethanol residue (31/69 cis/trans).

[0409] with 77.68g dimethyl terephthalate (DMT), 48.46g cyclohexanedimethanol, 17.86g 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyltin oxide place 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.This polyester is to prepare to the described similar mode of embodiment 1A.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 100.5 ℃, and logarithmic viscosity number is 0.73dl/g.NMR analysis revealed polymkeric substance comprises 80.5mol% cyclohexanedimethanol residue and 19.5mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1D

[0410] present embodiment illustrates the preparation that target group becomes the copolyesters of 100mol% dimethyl terephthalate (DMT) residue, 40mol% dimethyl isophthalate residue and 100mol% cyclohexanedimethanol residue (28/72 cis/trans).

[0411] mixture with 42.83g dimethyl terephthalate (DMT), 55.26g cyclohexanedimethanol, 28.45g dimethyl isophthalate and 0.0419g dibutyltin oxide places 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 290 ℃ in 5 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 60 minutes at 290 ℃, applied vacuum then gradually and press in flask and reach 100mmHg in ensuing 5 minutes.Again that the flask internal drop is low to 0.3mmHg in ensuing 5 minutes.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 81.2 ℃, and logarithmic viscosity number is 0.67dl/g.NMR analysis revealed polymkeric substance comprises 100mol% cyclohexanedimethanol residue and 40.2mol% dimethyl isophthalate residue.

Embodiment 1E

[0412] present embodiment illustrates the preparation that target group becomes the copolyesters of 100mol% dimethyl terephthalate (DMT) residue, 40mol% glycol residue and 60mol% cyclohexanedimethanol residue (31/69 cis/trans).

[0413] mixture with 81.3g dimethyl terephthalate (DMT), 42.85g cyclohexanedimethanol, 34.44g ethylene glycol and 0.0419g dibutyltin oxide places 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 200 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 210 ℃ in 60 minutes subsequently gradually 200 ℃ of heating in 5 minutes.Reaction mixture kept 120 minutes and arrived up to 280 ℃ at 30 minutes internal heating subsequently at 210 ℃.In case reach 280 ℃, in ensuing 5 minutes, apply vacuum gradually and in flask, press and reach 100mmHg.Again that the flask internal drop is low to 0.3mmHg in ensuing 10 minutes.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 82.1 ℃, and logarithmic viscosity number is 0.64dl/g.NMR analysis revealed polymkeric substance comprises the 34.5mol% glycol residue.

Embodiment 1F

[0414] present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 40mol%2, and 2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue and 60mol% cyclohexanedimethanol residue (31/69 cis/trans).

[0415] with 77.4g dimethyl terephthalate (DMT), 36.9g cyclohexanedimethanol, 32.5g2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyltin oxide place 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually and in flask, press and reach 100mmHg.Again that the flask internal drop is low to 0.3mmHg in ensuing 5 minutes.The pressure that keeps 0.3mmHg altogether 90 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 122 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 59.9mol% cyclohexanedimethanol residue and 40.1mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1G

[0416] present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 20mol%2,2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue (98/2 cis/trans) and 80mol% cyclohexanedimethanol residue (31/69 cis/trans).

[0417] with 77.68g dimethyl terephthalate (DMT), 48.46g cyclohexanedimethanol, 20.77g 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyltin oxide place 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually and in flask, press and reach 100mmHg, and also stirring velocity is dropped to 100RPM.In ensuing 5 minutes, again the flask internal drop is hanged down and drop to 50RPM to 0.3mmHg with stirring velocity.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 103 ℃, and logarithmic viscosity number is 0.65dl/g.NMR analysis revealed polymkeric substance comprises 85.7mol% cyclohexanedimethanol residue and 14.3mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 1H

[0418] present embodiment illustrates target group becomes 100mol% dimethyl terephthalate (DMT) residue, 20mol%2,2,4,4-tetramethyl--1, the preparation of the copolyesters of 3-cyclobutanediol residue (5/95 cis/trans) and 80mol% cyclohexanedimethanol residue (31/69 cis/trans).

[0419] with 77.68g dimethyl terephthalate (DMT), 48.46g cyclohexanedimethanol, 20.77g 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol and 0.046g dibutyltin oxide place 500 ml flasks that are equipped with nitrogen ingress pipe, metal agitator and short distillation column.Place the Wood's metal that is heated to 210 ℃ to bathe in flask.Stirring velocity is set at 200RPM in whole experiment.Content in the flask also was elevated to temperature 260 ℃ in 3 minutes subsequently gradually 210 ℃ of heating in 30 minutes.Reaction mixture kept 120 minutes and arrived up to 290 ℃ at 30 minutes internal heating subsequently at 260 ℃.In case reach 290 ℃, in ensuing 5 minutes, apply vacuum gradually and in flask, press and reach 100mmHg, and also stirring velocity is dropped to 100RPM.In ensuing 5 minutes, again the flask internal drop is hanged down and drop to 50RPM to 0.3mmHg with stirring velocity.The pressure that keeps 0.3mmHg altogether 60 minutes to remove excessive unreacted glycol.Notice that vacuum system does not reach above-mentioned setting point, but the vacuum that produces is enough to obtain high melt viscosity, transparent and colourless polymkeric substance visually, second-order transition temperature is 99 ℃, and logarithmic viscosity number is 0.73dl/g.NMR analysis revealed polymkeric substance comprises 85mol% cyclohexanedimethanol residue and 15mol%2, and 2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 2

[0420] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the 3-cyclobutanediol improves the flexible based on the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) of PCT.

[0421] preparation as described below is based on 2,2,4,4-tetramethyl--1, the copolyesters of 3-cyclobutanediol.For all samples, the cis/trans ratios of 1,4 cyclohexane dimethanol is about 31/69.Copolyesters based on ethylene glycol and 1,4 cyclohexane dimethanol is commercially available polyester.The copolyesters of embodiment 2A (Eastar PCTG 5445) obtains from Eastman Chemical Co..The copolyesters of embodiment 2B obtains with trade(brand)name Spectar from Eastman Chemical Co..Embodiment 2C and embodiment 2D prepare with the reprogramming of pilot scale (each 15-1b batch) according to the described program of embodiment 1A, and have logarithmic viscosity number shown in the following table 2 and second-order transition temperature.Embodiment 2C adopts target tin consumption (dibutyltin oxide) preparation of 300ppm.Final product comprises 295ppm tin.The colour of the polyester of embodiment 2C is L ^*=77.11; a ^*=-1.50; And b ^*=5.79.Embodiment 2D adopts target tin consumption (dibutyltin oxide) preparation of 300ppm.Final product comprises 307ppm tin.The colour of the polyester of embodiment 2D is L ^*=66.72; a ^*=-1.22; And b ^*=16.28.

[0422] material is injection molded into band sample and subsequently otch carry out izod test.Obtaining temperature variant notched izod impact strength also also is recorded in the table 2.

[0423] for given sample, izod impact strength is little main transformation of temperature range experience.For example, based on the izod impact strength of the copolyesters of 38mol% ethylene glycol in this transformation of 15-20 ℃ of experience.This transition temperature is relevant with the variation of failure mode; Fragility/low energy lost efficacy at lesser temps, and toughness/high energy lost efficacy at comparatively high temps.This transition temperature is expressed as the brittle-ductile transition temperature T _Bd, it is that flexible is measured.T _BdWrite down in table 2 and in Fig. 2, mapped with respect to comonomer mol%.

[0424] data show, with the T that has improved PCT _BdEthylene glycol compare, in PCT, add 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol has reduced T _BdAnd improved toughness.

Table 2

Notched izod impact energy (ft-lb/in)

Embodiment	Comonomer (mol%) ¹	IV (dl/g)	T _g (℃)	T _bd (℃)	-20 ℃	-15 ℃	-10 ℃	-5 ℃	0 ℃	5 ℃	10 ℃	15 ℃	20 ℃	25 ℃	30 ℃
Embodiment	Comonomer (mol%) ¹	IV (dl/g)	T _g (℃)	T _bd (℃)	-20 ℃	-15 ℃	-10 ℃	-5 ℃	0 ℃	5 ℃	10 ℃	15 ℃	20 ℃	25 ℃	30 ℃	2A	38.0％B	0.68	86	18	NA	NA	NA	1.5	NA	NA	1.5	1.5	32	32	NA
2B	69.0％B	0.69	82	26	NA	NA	NA	NA	NA	NA	2.1	NA	2.4	13.7	28.7	2A	38.0％B	0.68	86	18	NA	NA	NA	1.5	NA	NA	1.5	1.5	32	32	NA
2B	69.0％B	0.69	82	26	NA	NA	NA	NA	NA	NA	2.1	NA	2.4	13.7	28.7	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA
2D	42.8％C	0.60	133	-12	2.5	2.5	11	NA	14	NA	NA	NA	NA	NA	NA	2C	22.0％C	0.66	106	-5	1.5	NA	12	23	23	NA	23	NA	NA	NA	NA

The remainder of the diol component of polyester is a cyclohexanedimethanol in 1 this table.All polymkeric substance prepare by the 100mol% dimethyl terephthalate (DMT).

NA=does not obtain.

Wherein:

B is an ethylene glycol

C is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (50/50 cis/trans)

Embodiment 3

[0425] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises 2,2,4 of 15-25mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

[0426] preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, and the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition as shown in table 3 and performance.Surplus to the diol component of maximum 100mol% polyester is 1,4 cyclohexane dimethanol (31/69 cis/trans) in the table 3.

[0427] material is injection molded into the thick band sample of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain notched izod impact strength and be recorded in the table 3 at 23 ℃.Density, Tg and the hypocrystalline time of test molding band sample.Melt viscosity at 290 ℃ of test pellets.

Table 3

The various performances that can be used for some polyester of the present invention gather

Embodiment	TM CD mol ％	% cis TM CD	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TM CD mol ％	% cis TM CD	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	15	48.8	0.736	0.707	1069	878	1.184	104	15	5649
B	18	NA	0.728	0.715	980	1039	1.183	108	22	6621	A	15	48.8	0.736	0.707	1069	878	1.184	104	15	5649
B	18	NA	0.728	0.715	980	1039	1.183	108	22	6621	C	20	NA	0706	0.696	1006	1130	1.182	106	52	6321
D	22	NA	0.732	0.703	959	988	1.178	108	63	7161	C	20	NA	0706	0.696	1006	1130	1.182	106	52	6321
D	22	NA	0.732	0.703	959	988	1.178	108	63	7161	E	21	NA	0.715	0.692	932	482	1.179	110	56	6162
F	24	NA	0.708	0.677	976	812	1.180	109	58	6282	E	21	NA	0.715	0.692	932	482	1.179	110	56	6162
F	24	NA	0.708	0.677	976	812	1.180	109	58	6282	G	23	NA	0.650	0.610	647	270	1.182	107	46	3172
H	23	47.9	0.590	0549	769	274	1.181	106	47	1736	G	23	NA	0.650	0.610	647	270	1.182	107	46	3172
H	23	47.9	0.590	0549	769	274	1.181	106	47	1736	I	23	48.1	0.531	0.516	696	352	1.182	105	19	1292
J	23	47.8	0.364	NA	NA	NA	NA	98	NA	167	I	23	48.1	0.531	0.516	696	352	1.182	105	19	1292

NA=does not obtain.

Embodiment 3A

[0428] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mo1) dimethyl terephthalate (DMT), 14.34lb (45.21gram-mol) 1,4-cyclohexanedimethanol and 4.58lb (14.44gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reaction mixture remain on 290 ℃ and＜no longer increase (70 minutes) up to power traction under the pressure of 1mmHg to agitator.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.736dL/g and 104 ℃ Tg.NMR analysis revealed polymkeric substance comprises 85.4mol%1,4-cyclohexanedimethanol residue and 14.6mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=78.20; a ^*=-1.62; And b ^*=6.23.

Embodiment 3B-embodiment 3D

[0429] polyester described in the embodiment 3B-embodiment 3D is according to preparing to the described similar program of embodiment 3A.The composition and the performance of these polyester are shown in Table 3.

Embodiment 3E

[0430] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reaction mixture remain on 290 ℃ and＜following 60 minutes of the pressure of 1mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.715dL/g and 110 ℃ Tg.X-ray analysis shows that polyester has 223ppm tin.NMR analysis revealed polymkeric substance comprises 78.6mol%1,4-cyclohexanedimethanol residue and 21.4mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=76.45; a ^*=-1.65; And b ^*=6.47.

Embodiment 3F

[0431] polyester described in the embodiment 3F is according to preparing to the described similar program of embodiment 3A.The composition and the performance of this polyester are shown in Table 3.

Embodiment 3H

[0432] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reaction mixture remain on 290 ℃ and＜following 12 minutes of the pressure of 1mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.590dL/g and 106 ℃ Tg.NMR analysis revealed polymkeric substance comprises 77.1mol%1,4-cyclohexanedimethanol residue and 22.9mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=83.27; a ^*=-1.34; And b ^*=5.08.

Embodiment 3I

[0433] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 4mmHg.Reaction mixture is remained on following 30 minutes of the pressure of 290 ℃ and 4mmHg.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.531dL/g and 105 ℃ Tg.NMR analysis revealed polymkeric substance comprises 76.9mol%1,4-cyclohexanedimethanol residue and 23.1mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=80.42; a ^*=-1.28; And b ^*=5.13.

Embodiment 3J

[0434] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 12.61lb (39.77gram-mol) 1,4-cyclohexanedimethanol and 6.30lb (19.88gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then the temperature of reaction mixture is risen to 270 ℃ and pressure reduced to 90mmHg.After 270 ℃ and 90mmHg keep 1 hour, agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 4mmHg, use nitrogen immediately the pressure of pressurizing vessel to be elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.364dL/g and 98 ℃ Tg.NMR analysis revealed polymkeric substance comprises 77.5mol%1,4-cyclohexanedimethanol residue and 22.5mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=77.20; a ^*=-1.47; And b ^*=4.62.

Embodiment 4

[0435] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.Zhi Bei polyester comprises greater than 25mol%-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

[0436] preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, and the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol (31/69 cis/trans), it has composition as shown in table 4 and performance.Surplus to the diol component of maximum 100mol% polyester is 1,4 cyclohexane dimethanol (31/69 cis/trans) in the table 4.

[0437] material is injection molded into the thick band sample of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain notched izod impact strength and be recorded in the table 4 at 23 ℃.Density, Tg and the hypocrystalline time of test molding band sample.Melt viscosity at 290 ℃ of test pellets.

Table 4

Embodiment	TMCD mol％	Cis TMCD %	Pellet IV (dl/g)	Molding band sample IV (d1/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TMCD mol％	Cis TMCD %	Pellet IV (dl/g)	Molding band sample IV (d1/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	27	47.8	0.714	0.678	877	878	1.178	113	280	8312
B	31	NA	0.667	0.641	807	789	1.174	116	600	6592	A	27	47.8	0.714	0.678	877	878	1.178	113	280	8312

NA=does not obtain.

Embodiment 4A

[0438] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 11.82lb (37.28gram-mol) 1,4-cyclohexanedimethanol and 6.90lb (21.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Reaction mixture temperature is risen to 270 ℃ then, and pressure is reduced to 90mmHg.Reaction mixture after keeping 1 hour under the pressure of 270 ℃ and 90mmHg, is reduced to 15RPM with agitator speed, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to＜1mmHg.With reaction mixture remain on 290 ℃ and＜no longer increase (50 minutes) up to power traction under the pressure of 1mmHg to agitator.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.714dL/g and 113 ℃ Tg.NMR analysis revealed polymkeric substance comprises 73.3mol%1,4-cyclohexanedimethanol residue and 26.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 4B

[0439] polyester of embodiment 4B is according to preparing to the described similar program of embodiment 4A.The composition and the performance of these polyester are shown in Table 4.

Embodiment 5

[0440] present embodiment illustrates 2,2,4, and 4-tetramethyl--1,3-cyclobutanediol can improve the toughness of the copolyesters (polyester that comprises terephthalic acid and 1,4 cyclohexane dimethanol) based on PCT.

[0441] preparation as described below is based on dimethyl terephthalate (DMT), 2,2,4,4-tetramethyl--1, and the copolyesters of 3-cyclobutanediol and 1,4 cyclohexane dimethanol, it has composition as shown in table 5 and performance.Surplus to the diol component of maximum 100mol% polyester is 1,4 cyclohexane dimethanol (31/69 cis/trans) in the table 5.

[0442] material is injection molded into the thick band sample of 3.2mm and 6.4mm and subsequently otch carry out izod impact test.Obtain notched izod impact strength and be recorded in the table 5 at 23 ℃.Density, Tg and the hypocrystalline time of test molding band sample.Melt viscosity at 290 ℃ of test pellets.

Table 5

Embodiment	TM CD mol ％	% cis TM CD	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec
Embodiment	TM CD mol ％	% cis TM CD	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	In the hypocrystalline time of 170 ℃ of melts (min)	Melt viscosity (pool) under 290 ℃ of 1rad/sec	A	44	46.2	0.657	0.626	727	734	1.172	119	NA	9751

NA=does not obtain.

Embodiment 5A

[0443] in the presence of 200ppm catalyzer three (2 ethyl hexanoic acid) butyl tin, make 21.24lb (49.71gram-mol) dimethyl terephthalate (DMT), 8.84lb (27.88gram-mol) 1,4-cyclohexanedimethanol and 10.08lb (31.77gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol one reacts.Be reflected under the nitrogen purging and in 18 gallons of stainless steel pressurizing vessels being furnished with condensation tower, vacuum system and HELICONE type agitator, carry out.Along with agitator turns round with 25RPM, reaction mixture temperature is elevated to 250 ℃, and pressure is elevated to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.With the speed of 3psig/min pressure is reduced to 0psig then.Then agitator speed is reduced to 15RPM, reaction mixture temperature is risen to 290 ℃, and pressure is reduced to 2mmHg.Reaction mixture is remained under the pressure of 290 ℃ and 2mmHg and no longer increase (80 minutes) up to power traction to agitator.Use nitrogen that the pressure of pressurizing vessel is elevated to 1 normal atmosphere then.From pressurizing vessel, extrude molten polymer subsequently.Grind the refrigerative extruded polymer by the 6-mm screen cloth.Polymkeric substance has the logarithmic viscosity number of 0.657dL/g and 119 ℃ Tg.NMR analysis revealed polymkeric substance comprises 56.3mol%1,4-cyclohexanedimethanol residue and 43.7mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.The colour of polyester is L ^*=75.04; a ^*=-1.82; And b ^*=6.72.

Embodiment 6-Comparative Examples

[0444] data that are used for contrast material shown in the present embodiment are shown in Table 6.PC is the Makrolon 2608 from Bayer, and its nominal consists of 100mol% dihydroxyphenyl propane residue and 100mol% dipheryl carbonate base ester residue.Makrolon 2608 has the nominal melt flow of use 1.2kg weight at the 20g/10min of 300 ℃ of mensuration.PET is the Eastar 9921 from Eastman ChemicalCompany, and its nominal consists of 100mol% terephthalic acid, 3.5mol% cyclohexanedimethanol (CHDM) and 96.5mol% ethylene glycol.PETG is the Eastar 6763 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% ethylene glycol.PCTG is the Eastar DN001 from EastmanChemical Company, and its nominal consists of 100mol% terephthalic acid, 62mol% cyclohexanedimethanol (CHDM) and 38mol% ethylene glycol.PCTA is the Eastar AN001 from Eastman Chemical Company, and its nominal consists of 65mol% terephthalic acid, 35mol% m-phthalic acid and 100mol% cyclohexanedimethanol (CHDM).Polysulfones is the Udel 1700 from Solvay, and its nominal consists of 100mol% dihydroxyphenyl propane and 100mol%4,4-two chlorosulfonyl sulfone residues.Udel 1700 has the nominal melt flow of use 2.16kg weight at the 6.5g/10min of 343 ℃ of mensuration.SAN is the Lustran 31 from Lanxess, and its nominal consists of 76mol% vinylbenzene and 24mol% vinyl cyanide.Lustran 31 has the nominal melt flow of use 3.8kg weight at the 7.5g/10min of 230 ℃ of mensuration.Compare with all other resins, embodiments of the invention demonstrate improved toughness in the thick band sample of 6.4mm.

Table 6

The various performances of some commercial polymer gather

Embodiment	The polymkeric substance title	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The hypocrystalline time (min) of melt
Embodiment	The polymkeric substance title	Pellet IV (dl/g)	Molding band sample IV (dl/g)	3.2mm thick band sample is 23 ℃ notched izod (J/m)	6.4mm thick band sample is 23 ℃ notched izod (J/m)	Proportion (g/mL)	Tg (℃)	The hypocrystalline time (min) of melt	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NA	70	1.23	87	170℃30	A	PC	12MFR	NA	929	108	1.20	146	NA
B	PCTG	0.73	0.696	NA	70	1.23	87	170℃30	C	PCTA	0.72	0.702	98	59	1.20	87	150℃15
D	PETG	0.75	0.692	83	59	1.27	80	130℃2500	C	PCTA	0.72	0.702	98	59	1.20	87	150℃15
D	PETG	0.75	0.692	83	59	1.27	80	130℃2500	E	PET	0.76	0.726	45	48	1.33	78	170℃1.5
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	E	PET	0.76	0.726	45	48	1.33	78	170℃1.5
F	SAN	7.5MFR	NA	21	NA	1.07	～110	NA	G	PSU	6.5MFR	NA	69	NA	1.24	～190	NA

NA=does not obtain.

Embodiment 7

[0445] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises 2,2,4 of 15-25mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment 7A-embodiment 7G

[0446] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.To 2,2,4,4-tetramethyl--1, the raw-material NMR analysis revealed of 3-cyclobutanediol cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough dibutyltin oxide catalyzer in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases and the reduction stir speed (S.S.), 15RPM is used minimum stir speed (S.S.).Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing material up to from glass flask, taking out.Stirring polymer masses with medium level in flask cools off up to polymkeric substance.Taking out polymkeric substance and grind from flask makes it pass through the 3mm screen cloth.This program is changed the copolyesters that becomes 20mol% with the target group of production the following stated.

[0447] as measurement logarithmic viscosity number as described in above " testing method " part.The composition of polyester as described in the Test Methods section in front by ¹H NMR measures.Second-order transition temperature is used to add heat determination the second time after the speed quenching of 20 ℃/min by DSC.

Embodiment 7H-embodiment 7Q

[0448] these polyester are by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is being carried out in the temperature reaction device (CTR) continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.In this reactor, add 777g (4mol) dimethyl terephthalate (DMT), 230g (1.6mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol, 460.8g (3.2mol) cyclohexanedimethanol and 1.12g three (2 ethyl hexanoic acid) butyl tin (make and in final polymkeric substance, have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Camile method Controlling System makes setting point and data gathering more convenient.In case the reactant fusion then begins to stir and slowly be increased to 250rpm.The temperature of reactor raises gradually along with runtime.The methyl alcohol weight of equaling a record and collecting by the sky.When the progress of methyl alcohol stops or in 260 ℃ lesser temps termination reaction of preliminary election.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, so that can be weighed in the 500ml round-bottomed flask.

[0449] in polycondensation, in the 500ml round-bottomed flask, adds the oligopolymer for preparing above about 150g.This flask is equipped with stainless steel agitator and cap.Glassware is arranged on the last and startup Camile sequence of half moles of polymer suite of equipment (a half mole polymer rig).In case the oligopolymer fusion is orientated agitator as from the drag meter full up position (full turn).For each embodiment by the temperature/pressure/stir speed (S.S.) sequential recording of Camile software control in following table.

[0450] the Camile sequence of embodiment 7H and embodiment 7I

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	6	25	5	110	290	90	50
6	5	290	6	25	7	110	290	6	25

[0451] the Camile sequence of embodiment 7N-embodiment 7Q

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	3	25	5	110	290	90	50
6	5	290	3	25	7	110	290	3	25

[0452] the Camile sequence of embodiment 7K and embodiment 7L

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	2	25	5	110	290	90	50
6	5	290	2	25	7	110	290	2	25

[0453] the Camile sequence of embodiment 7J and embodiment 7M

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	1	25	5	110	290	90	50
6	5	290	1	25	7	110	290	1	25

[0454] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and grind to form the 6mm screen mesh size.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).By ¹H NMR obtains polymkeric substance and forms.Use Rheometrics MechanicalSpectrometer (RMS-800) that sample is carried out thermostability and melt viscosity test.

[0455] following table has shown the experimental data of the polyester of present embodiment.These data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol content has improved second-order transition temperature in almost linear mode.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.

Table 7

The relation of second-order transition temperature and logarithmic viscosity number and composition

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g (℃)	260℃ η _o(pool)	275℃η _o(pool)	290℃ η _o(pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g (℃)	260℃ η _o(pool)	275℃η _o(pool)	290℃ η _o(pool)	A	20	51.4	0.72	109	11356	19503	5527
B	19.1	51.4	0.60	106	6891	3937	2051	A	20	51.4	0.72	109	11356	19503	5527
B	19.1	51.4	0.60	106	6891	3937	2051	C	19	53.2	0.64	107	8072	4745	2686
D	18.8	54.4	0.70	108	14937	8774	4610	C	19	53.2	0.64	107	8072	4745	2686
D	18.8	54.4	0.70	108	14937	8774	4610	E	17.8	52.4	0.50	103	3563	1225	883
F	17.5	51.9	0.75	107	21160	10877	5256	E	17.8	52.4	0.50	103	3563	1225	883
F	17.5	51.9	0.75	107	21160	10877	5256	G	17.5	52	0.42	98	NA	NA	NA
H	22.8	53.5	0.69	109	NA	NA	NA	G	17.5	52	0.42	98	NA	NA	NA
H	22.8	53.5	0.69	109	NA	NA	NA	I	22.7	52.2	0.68	108	NA	NA	NA
J	23.4	52.4	0.73	111	NA	NA	NA	I	22.7	52.2	0.68	108	NA	NA	NA
J	23.4	52.4	0.73	111	NA	NA	NA	K	23.3	52.9	0.71	111	NA	NA	NA
L	23.3	52.4	0.74	112	NA	NA	NA	K	23.3	52.9	0.71	111	NA	NA	NA
L	23.3	52.4	0.74	112	NA	NA	NA	M	23.2	52.5	0.74	112	NA	NA	NA
N	23.1	52.5	0.71	111	NA	NA	NA	M	23.2	52.5	0.74	112	NA	NA	NA
N	23.1	52.5	0.71	111	NA	NA	NA	O	22.8	52.4	0.73	112	NA	NA	NA
P	22.7	53	0.69	112	NA	NA	NA	O	22.8	52.4	0.73	112	NA	NA	NA
P	22.7	53	0.69	112	NA	NA	NA	Q	22.7	52	0.70	111	NA	NA	NA

NA=does not obtain.

Embodiment 8

[0456] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of the second-order transition temperature of polyester.Zhi Bei polyester comprises greater than 25-less than 2,2,4 of 40mol% in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

[0457] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.To 2,2,4,4-tetramethyl--1, the raw-material NMR analysis revealed of 3-cyclobutanediol cis/trans ratios is 53/47.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough dibutyltin oxide catalyzer in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases and the reduction stir speed (S.S.), 15RPM is used minimum stir speed (S.S.).Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing material up to from glass flask, taking out.Stirring polymer masses with medium level in flask cools off up to polymkeric substance.Taking out polymkeric substance and grind from flask makes it pass through the 3mm screen cloth.This program is changed the copolyesters that becomes 32mol% with the target group of production the following stated.

[0458] as measurement logarithmic viscosity number as described in above " testing method " part.The composition of polyester as described in the Test Methods section in front by ¹H NMR measures.Second-order transition temperature is used to add heat determination the second time after the speed quenching of 20 ℃/min by DSC.

[0459] following table has shown the experimental data of the polyester of present embodiment.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.These data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol content has improved second-order transition temperature in almost linear mode.

Table 8

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	A	32.2	51.9	0.71	118	29685	16074	8522
B	31.6	51.5	0.55	112	5195	2899	2088	A	32.2	51.9	0.71	118	29685	16074	8522
B	31.6	51.5	0.55	112	5195	2899	2088	C	31.5	50.8	0.62	112	8192	4133	2258
D	30.7	50.7	0.54	111	4345	2434	1154	C	31.5	50.8	0.62	112	8192	4133	2258
D	30.7	50.7	0.54	111	4345	2434	1154	E	30.3	51.2	0.61	111	7929	4383	2261
F	30.0	51.4	0.74	117	31476	17864	8630	E	30.3	51.2	0.61	111	7929	4383	2261
F	30.0	51.4	0.74	117	31476	17864	8630	G	29.0	51.5	0.67	112	16322	8787	4355
H	31.1	51.4	0.35	102	NA	NA	NA	G	29.0	51.5	0.67	112	16322	8787	4355

NA=does not obtain.

Embodiment 9

[0460] present embodiment illustrates and is used to prepare 2,2,4 of polyester of the present invention, 4-tetramethyl--1, and the consumption of 3-cyclobutanediol is to the influence of polyester second-order transition temperature.To comprise consumption be 40mol% or bigger by 2,2,4 to Zhi Bei polyester in the present embodiment, 4-tetramethyl--1,3-cyclobutanediol residue.

Embodiment A-C

[0461] these polyester are by carrying out transesterify in the stage of separating and polycondensation prepares.The transesterify experiment is being carried out in the temperature reaction device (CTR) continuously.CTR is equipped with single shaft impeller blade agitator, is covered with electric mantle and is furnished with the 3000ml glass reactor of the filling reflux condensation mode post of heating.In this reactor, add 777g dimethyl terephthalate (DMT), 375g 2,2,4,4-tetramethyl--1,3-cyclobutanediol, 317g cyclohexanedimethanol and 1.12g three (2 ethyl hexanoic acid) butyl tin (make and in final polymkeric substance, have the 200ppm tin metal).It is 100% output that heating jacket manually is set.Camile method Controlling System makes setting point and data gathering more convenient.In case the reactant fusion then begins to stir and slowly be increased to 250rpm.The temperature of reactor raises gradually along with runtime.The methyl alcohol weight of equaling a record and collecting by the sky.When the progress of methyl alcohol stops or in 260 ℃ lesser temps termination reaction of preliminary election.Adopt nitrogen purging to discharge oligopolymer and cool to room temperature.Adopt the liquid nitrogen freezing oligopolymer and be broken into enough little fritter, so that can be weighed in the 500ml round-bottomed flask.

[0462] in polycondensation, in the 500ml round-bottomed flask, adds the oligopolymer for preparing above the 150g.This flask is equipped with stainless steel agitator and cap.Be arranged on glassware on the half moles of polymer suite of equipment and start the Camile sequence.In case the oligopolymer fusion is orientated agitator as from the drag meter full up position.For each embodiment, by the temperature/pressure/stirring speed sequential recording of Camile software control in following table, unless in following other explanation.

The Camile sequence of polycondensation

[0463] the Camile sequence of embodiment A and B

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	6	25	5	110	290	90	50
6	5	290	6	25	7	80	290	6	25

[0464] for Embodiment C, in the use table in identical sequence, but in the stage 7 time be 50 minutes.

[0465] from flask, reclaims resulting polymers, use the chopping of hydraulic pressure knife mill, and grind to form the 6mm screen mesh size.Sample to the polymkeric substance of each grinding carries out following test: measure logarithmic viscosity number in 60/40 (wt/wt) phenol/tetrachloroethane, measure levels of catalysts (Sn) and obtain color (L by transmitted spectrum by XRF 25 ℃ of concentration with 0.5g/100ml ^*, a ^*, b ^*).By ¹H NMR obtains polymkeric substance and forms.Use Rheometrics MechanicalSpectrometer (RMS-800) that sample is carried out thermostability and melt viscosity test.

Embodiment D-K and M

[0466] for preparation as described in embodiment A-C, but for embodiment D-K and M, the consumption of target tin is 150ppm to the polyester of these embodiment in final polymkeric substance as above.Following table has been put down in writing the temperature/pressure/stir speed (S.S.) sequence by the Camile software control for these embodiment.

[0467] the Camile sequence of embodiment D, F and H

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	400	50	3	30	265	760	50
4	3	265	400	50	5	110	290	400	50
6	5	290	8	50	5	110	290	400	50
6	5	290	8	50	7	110	295	8	50

[0468] for embodiment D, agitator goes to 25rpm 95min in the stage 7.

[0469] the Camile sequence of embodiment E

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	10	245	760	0
2	5	245	760	50	1	10	245	760	0
2	5	245	760	50	3	30	283	760	50
4	3	283	175	50	3	30	283	760	50
4	3	283	175	50	5	5	283	5	50
6	5	283	1.2	50	5	5	283	5	50
6	5	283	1.2	50	7	71	285	1.2	50

[0470] for embodiment K, in the use table in identical sequence, but in the stage 7 time be 75 minutes.

[0471] the Camile sequence of embodiment G

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	10	245	760	0
2	5	245	760	50	1	10	245	760	0
2	5	245	760	50	3	30	285	760	50
4	3	285	175	50	3	30	285	760	50
4	3	285	175	50	5	5	285	5	50
6	5	285	4	50	5	5	285	5	50
6	5	285	4	50	7	220	290	4	50

[0472] the Camile sequence of example I

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	285	90	50
6	5	285	6	50	5	110	285	90	50
6	5	285	6	50	7	70	290	6	50

[0473] the Camile sequence of embodiment J

Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)
Stage	Time (min)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (rpm)	1	5	245	760	0
2	5	245	760	50	1	5	245	760	0
2	5	245	760	50	3	30	265	760	50
4	3	265	90	50	3	30	265	760	50
4	3	265	90	50	5	110	290	90	50
6	5	290	6	25	5	110	290	90	50
6	5	290	6	25	7	110	295	6	25

Embodiment L and K

[0474] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-ml.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough dibutyltin oxide catalyzer in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases and the reduction stir speed (S.S.), 15RPM is used minimum stir speed (S.S.).Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing material up to from glass flask, taking out.Stirring polymer masses with medium level in flask cools off up to polymkeric substance.Taking out polymkeric substance and grind from flask makes it pass through the 3mm screen cloth.This program is changed the copolyesters that becomes 45mol% with the target group of production the following stated.

[0475] as measurement logarithmic viscosity number as described in above " testing method " part.The composition of polyester as described in the Test Methods section in front by ¹H NMR measures.Second-order transition temperature is used to add heat determination the second time after the speed quenching of 20 ℃/min by DSC.

[0476] following table has shown the experimental data of the polyester of present embodiment.These data show, for the constant logarithmic viscosity number, and 2,2,4,4-tetramethyl--1, the increase of 3-cyclobutanediol content has improved second-order transition temperature in almost linear mode.Fig. 3 also shows the dependency of Tg to composition and logarithmic viscosity number.

Table 9

Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)
Embodiment	mol％ TMCD	% cis TMCD	IV (dL/g)	T _g(℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	A	44.2	36.4	0.49	118	NA	NA	NA
B	44.3	36.3	0.51	119	NA	NA	NA	A	44.2	36.4	0.49	118	NA	NA	NA
B	44.3	36.3	0.51	119	NA	NA	NA	C	44.4	35.6	0.55	118	NA	NA	NA
D	46.3	52.4	0.52	NA	NA	NA	NA	C	44.4	35.6	0.55	118	NA	NA	NA
D	46.3	52.4	0.52	NA	NA	NA	NA	E	45.7	50.9	0.54	NA	NA	NA	NA
F	463	52.6	0.56	NA	NA	NA	NA	E	45.7	50.9	0.54	NA	NA	NA	NA
F	463	52.6	0.56	NA	NA	NA	NA	G	46	50.6	0.56	NA	NA	NA	NA
H	465	51.8	0.57	NA	NA	NA	NA	G	46	50.6	0.56	NA	NA	NA	NA
H	465	51.8	0.57	NA	NA	NA	NA	I	45.6	51.2	0.58	NA	NA	NA	NA
J	46	51.9	0.58	NA	NA	NA	NA	I	45.6	51.2	0.58	NA	NA	NA	NA
J	46	51.9	0.58	NA	NA	NA	NA	K	455	51.2	0.59	NA	NA	NA	NA
L	46.1	49.6	0.383	117	NA	NA	NA	K	455	51.2	0.59	NA	NA	NA	NA
L	46.1	49.6	0.383	117	NA	NA	NA	K	45.6	50.5	0.325	108	NA	NA	NA
M	47.2	NA	0.48	NA	NA	NA	NA	K	45.6	50.5	0.325	108	NA	NA	NA

NA=does not obtain.

Embodiment 10

[0477] present embodiment illustrates 2,2,4,4-tetramethyl--1, and the type advantage of 3-cyclobutanediol isomer (cis or trans) is to the influence of the second-order transition temperature of polyester.

[0478] with dimethyl terephthalate (DMT), 1,4 cyclohexane dimethanol and 2,2,4,4-tetramethyl--1,3-cyclobutanediol are weighed in the single neck round-bottomed flask of 500-m1.The polyester of present embodiment adopts 1.2/1 glycol/sour ratio preparation, and is all excessive all from 2,2,4,4-tetramethyl--1,3-cyclobutanediol.Add enough dibutyltin oxide catalyzer in final polymkeric substance, to obtain 300ppm tin.Flask is under the 0.2SCFC nitrogen purging with the low ability of vacuum drop.Flask is immersed 200 ℃ Belmont metal bath and after the reactant fusion, stir with 200RPM.After about 2.5 hours, temperature is increased to 210 ℃ and these conditions were kept other 2 hours.Temperature is increased to 285 ℃ (about 25 minutes) and in 5 minutes pressure is reduced to 0.3mmHg.Along with viscosity increases and the reduction stir speed (S.S.), 15RPM is used minimum stir speed (S.S.).Change the total polymerization time to obtain the target logarithmic viscosity number.After polymerization is finished, reduce the Belmont metal bath and allow polymkeric substance to be cooled to be lower than its second-order transition temperature.After about 30 minutes, once more flask is immersed Belmont metal bath (temperature has risen to 295 ℃ in this waiting time of 30 minutes) and heated polymerizable thing material up to from glass flask, taking out.Stirring polymer masses with medium level in flask cools off up to polymkeric substance.Taking out polymkeric substance and grind from flask makes it pass through the 3mm screen cloth.This program is changed the copolyesters that becomes 45mol% with the target group of production the following stated.

[0479] as measurement logarithmic viscosity number as described in above " testing method " part.The composition of polyester as described in the Test Methods section in front by ¹H NMR measures.Second-order transition temperature is used to add heat determination the second time after the speed quenching of 20 ℃/min by DSC.

[0480] following table has shown the experimental data of the polyester of present embodiment.These data show, for the constant logarithmic viscosity number, improving aspect the second-order transition temperature, and cis 2,2,4,4-tetramethyl--1, it is trans 2,2,4 that the validity of 3-cyclobutanediol is about, 4-tetramethyl--1, the twice of 3-cyclobutanediol.

Table 10

2,2,4,4-tetramethyl--1,3-cyclobutanediol cis/trans is formed the influence to Tg

Embodiment	mol％ TMCD	IV (dL/g)	T _g (℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	% cis TMCD
Embodiment	mol％ TMCD	IV (dL/g)	T _g (℃)	260℃ η _o(pool)	275℃ η _o(pool)	290℃ η _o(pool)	% cis TMCD	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A.	N.A.	22.0	A	45.8	0.71	119	N.A.	N.A.	N.A.	4.1
B	43.2	0.72	122	N.A.	N.A.	N.A.	22.0	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	C	46.8	0.57	119	26306	16941	6601	22.8
D	43.0	0.67	125	55060	36747	14410	23.8	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	E	43.8	0.72	127	101000	62750	25330	24.5
F	45.9	0.533	119	11474	6864	2806	26.4	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A.	29.0	G	45.0	0.35	107	N.A.	N.A.	N.A.	27.2
H	41.2	0.38	106	1214	757	N.A.	29.0	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	I	44.7	0.59	123	N.A.	N.A.	N.A.	35.4
J	44.4	0.55	118	N.A.	N.A.	N.A.	35.6	K	44.3	0.51	119	N.A.	N.A.	N.A.	36.3
L	44.0	0.49	128	N.A.	N.A.	N.A.	71.7	K	44.3	0.51	119	N.A.	N.A.	N.A.	36.3
L	44.0	0.49	128	N.A.	N.A.	N.A.	71.7	M	43.6	0.52	128	N.A.	N.A.	N.A.	72.1
N	43.6	0.54	127	N.A.	N.A.	N.A.	72.3	M	43.6	0.52	128	N.A.	N.A.	N.A.	72.1
N	43.6	0.54	127	N.A.	N.A.	N.A.	72.3	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	O	41.5	0.58	133	15419	10253	4252	88.7
P	43.8	0.57	135	16219	10226	4235	89.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	Q	41.0	0.33	120	521	351	2261	90.4
R	43.0	0.56	134	N.A.	N.A.	N.A.	90.6	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	S	43.0	0.49	132	7055	4620	2120	90.6
T	43.1	0.55	134	12970	8443	3531	91.2	U	45.9	0.52	137	N.A.	N.A.	N.A.	981

NA=does not obtain.

Embodiment 11-Comparative Examples

[0481] present embodiment illustrates based on 100%2,2,4, and 4-tetramethyl--1, the polyester of 3-cyclobutanediol have the hypocrystalline time slowly.

[0482] with the preparation of the similar method of method described in the embodiment 1A only based on terephthalic acid and 2,2,4,4-tetramethyl--1, the polyester of 3-cyclobutanediol, performance is shown in Table 11.Adopt the 300ppm dibutyltin oxide to prepare this polyester.2,2,4,4-tetramethyl--1, the cis/trans ratios of 3-cyclobutanediol are 65/35.

[0483] 320 ℃ of polymkeric substance press membrane by grinding.Be the hypocrystalline time of increment measurement melt with 10 ℃ and be recorded in the table 11 at 220-250 ℃.Get the minimum value of the fastest hypocrystalline time of every kind of sample as the temperature variant hypocrystalline time.The fastest hypocrystalline time of this polyester is about 1300 minutes.This value with as shown in Figure 1 only have the extremely short hypocrystalline time (＜1min) true opposite based on the polyester (PCT) of terephthalic acid and 1,4 cyclohexane dimethanol (no comonomer modification).

Table 11

The hypocrystalline time (min)

Comonomer (mol%)	IV (dl/g)	Tg (℃)	T _max (℃)	220℃ (min)	230℃ (min)	240℃ (min)	250℃ (min)
Comonomer (mol%)	IV (dl/g)	Tg (℃)	T _max (℃)	220℃ (min)	230℃ (min)	240℃ (min)	250℃ (min)	100mol％F	0.63	170.0	330	3291	3066	1303	1888

Wherein F is 2,2,4,4-tetramethyl--1,3-cyclobutanediol (65/35 cis/trans)

Embodiment 12

[0484] use 3.5 inches single screw extrusion machine productions to comprise the thin plate of polyester, described polyester prepares, and its target group becomes 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to size.On a thin plate, measure logarithmic viscosity number and second-order transition temperature.The logarithmic viscosity number of measuring thin plate is 0.69dL/g.The second-order transition temperature of measuring thin plate is 106 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment G).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoforming thin plates with 106 ℃ of second-order transition temperatures can thermoforming under condition shown below, has at least 95% stretching and non-foaming proof by these thin plates, need not before thermoforming predrying.

Embodiment 13

[0485] use 3.5 inches single screw extrusion machine productions to comprise the thin plate of polyester, described polyester prepares, and its target group becomes 100mol% terephthalic acid residue, 80mol%1,4-cyclohexanedimethanol residue and 20mol%2,2,4,4-tetramethyl--1,3-cyclobutanediol residue.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to size.On a thin plate, measure logarithmic viscosity number and second-order transition temperature.The logarithmic viscosity number of measuring thin plate is 0.69dL/g.The second-order transition temperature of measuring thin plate is 106 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 60/40/40% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment G).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoforming thin plates with 106 ℃ of second-order transition temperatures can thermoforming under condition shown below, has at least 95% extensibility and non-foaming proof by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 14-Comparative Examples

[0486] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Kelvx is by 69.85%PCTG (from the Eastar of Eastman Chemical Co., having 100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue); 30%PC (bisphenol-a polycarbonate); The blend of forming with 0.15%Weston 619 (stablizer of selling by CromptonCorporation).Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 100 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 2 weeks of conditioning.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment E).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 100 ℃ of second-order transition temperatures can thermoforming under condition shown below, has at least 95% extensibility and non-foaming proof by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 15-Comparative Examples

[0487] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Kelvx 201.Extrude thin plate continuously, measuring thickness is 177 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 100 ℃.Then with thin plate in 100% relative humidity and 25 ℃ 2 weeks of conditioning.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 60/40/40% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment H).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 100 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

NR=is record not

Embodiment 16-Comparative Examples

[0488] thin plate that uses 3.5 inches single screw extrusion machine productions to form by PCTG 25976 (100mol% terephthalic acid residue, 62mol%1,4-cyclohexanedimethanol residue and 38mol% glycol residue).Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 87 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.17wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 87 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 17-Comparative Examples

[0489] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 20wt%Teijin L-1250 polycarbonate (bisphenol-a polycarbonate), 79.85wt%PCTG 25976 and 0.15wt%Weston619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 94 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.25wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 94 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 18-Comparative Examples

[0490] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 30wt%Teijin L-1250 polycarbonate, 69.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 99 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.25wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 99 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

NA=is inapplicable.0 value shows and does not form this thin plate, because it can not be drawn in mould (may be because too cold).

Embodiment 19-Comparative Examples

[0491] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 40wt%Teijin L-1250 polycarbonate, 59.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 105 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.265wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment 8A-8E).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 105 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 20-Comparative Examples

[0492] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 50wt%Teijin L-1250 polycarbonate, 49.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 111 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.225wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by at this group experiment (maximum part volume of acquisition in the embodiment A-D).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 111 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 21-Comparative Examples

[0493] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 60wt%Teijin L-1250 polycarbonate, 39.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 117 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.215wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 117 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 22-Comparative Examples

[0494] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 65wt%Teijin L-1250 polycarbonate, 34.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 120 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.23wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 120 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 23-Comparative Examples

[0495] uses 1.25 inches miscible blends that single screw extrusion machine production is made up of 70wt%Teijin L-1250 polycarbonate, 29.85wt%PCTG 25976 and 0.15wt%Weston 619.The thin plate that uses 3.5 inches single screw extrusion machine productions to form then by this blend.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 123 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.205wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A and B).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 123 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 24-Comparative Examples

[0496] uses 3.5 inches thin plates that single screw extrusion machine production is made up of Teijin L-1250 polycarbonate.Extrude thin plate continuously, measuring thickness is 118 mils, then various Shears for thin sheets is switched to size.The second-order transition temperature of measuring on a thin plate is 149 ℃.Then with thin plate in 50% relative humidity and 60 ℃ 4 weeks of conditioning.The mensuration moisture content is 0.16wt%.Using Blang's thermoforming machine that sheet thermol formation is become stretch ratio subsequently is 2.5: 1 former.Only use top heat that thermoforming stove well heater is set at 70/60/60% output.Thin plate is trapped in the time different in the stove, so that it is determine of the influence of thin plate temperature, as shown in the table to part quality.Part quality is determined by volume, calculating extensibility and the visual inspection thermoforming parts of measuring the thermoforming parts.Extensibility is calculated as piece volumes divided by the maximum part volume that obtains in this group experiment (embodiment A).Whether visual inspection thermoforming parts have any foaming, and the foaming grading is nothing (N), low (L) or high (H).Following result proves, these thermoplastic sheet with 149 ℃ of second-order transition temperatures can thermoforming under condition shown below, has extensibility and non-foaming proof greater than 95% by the thin plate of producing, and need not before thermoforming predrying.

Embodiment 25

[0497] present embodiment illustrates the preparation method of the polyester that comprises at least a thermo-stabilizer, its reaction product and composition thereof, obtains improved polyester fondant stability in the course of processing.

[0498] various polyester according to the following stated method from 100mol% dimethyl terephthalate (DMT) (DMT), 1,4 cyclohexane dimethanol (CHDM) and 2,2,4,4-tetramethyl--1,3-tetramethylene glycol (TMCD) preparation.The mol% that is used for the TMCD of present embodiment experiment is recorded in following table 12, and wherein the glycol surplus is CHDM.DMT buys from Cape Industries, and CHDM (minimum concentration 98%) and TMCD (minimum concentration 98%) are purchased from Eastman Chemical Company.Tin compound is cacodyl oxide base tin (from Strem Chemical Co. or Gelest, Inc. obtains) or three-2 ethyl hexanoic acid butyl tin (obtaining from Aldrich or Arkema).Phosphorus compound is Triphenyl phosphate (TPP, from Aldrich (98%) or FERRO, Corp. obtains).Unless explanation is below arranged in addition, the source of phosphorus is that the remainder with polyester reagent adds in advance.The cis/trans ratios of CHDM as previously discussed, and the cis/trans ratios of TMCD is recorded in the table 12.

Table 12

The composition of the polyester of embodiment 25 and logarithmic viscosity number

Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)
Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)	A	0.605	44.8	50.0	205 ¹	Do not have	*	290
B	0.583	44.4	51.9	201 ¹	Do not have	*	290	A	0.605	44.8	50.0	205 ¹	Do not have	*	290
B	0.583	44.4	51.9	201 ¹	Do not have	*	290	C	0.578	43.9	50.7	199 ¹	Do not have	*	290
D	0607	44.9	50.5	199 ²	Do not have	*	290	C	0.578	43.9	50.7	199 ¹	Do not have	*	290
D	0607	44.9	50.5	199 ²	Do not have	*	290	E	0.437	44.5	52.0	200 ²	Do not have	*	290
F	0.292	44.8	51.9	190 ²	34/34	5.6	290	E	0.437	44.5	52.0	200 ²	Do not have	*	290
F	0.292	44.8	51.9	190 ²	34/34	5.6	290	G	0.580	45.1	50.5	192 ¹	10/11	17.5	290
H	0.541	44.0	52.3	202 ²	19/20	10.1	290	G	0.580	45.1	50.5	192 ¹	10/11	17.5	290
H	0.541	44.0	52.3	202 ²	19/20	10.1	290	I	0.595	45.3	50.6	198 ²	20/20	9.9	290
J	0.632	45.6	49.0	203 ²	20/22	9.2	265	I	0.595	45.3	50.6	198 ²	20/20	9.9	290
J	0.632	45.6	49.0	203 ²	20/22	9.2	265	K	0.577	46.2	50.1	196 ²	30/26	7.5	265
L	0.608	46.0	49.6	190 ¹	20/19	10.0	265	K	0.577	46.2	50.1	196 ²	30/26	7.5	265
L	0.608	46.0	49.6	190 ¹	20/19	10.0	265	M	0.517	45.2	49.4	100 ²	10/10	10.0	265
N	0.602	46.1	49.2	102 ²	10/10	10.2	265	M	0.517	45.2	49.4	100 ²	10/10	10.0	265

1 three-2 ethyl hexanoic acid butyl tin is as the source of tin

2 cacodyl oxide base tin are as the source of tin

[0499] data in the table 13 show, if use identical condition on pilot scale or technical scale, think that then the stability of polymer melt of comparative example A-D is unacceptable.On the contrary, stable melt is produced in the experiment with suitable tin/phosphorus ratio, is fit to the method for amplifying in proportion.

Table 13

The performance of the polyester of embodiment 25

Embodiment	L ^*	a ^*	b ^*	Melt liquid level stability	The polymer color observations	% foam in polyester	The vision grading of polyester
Embodiment	L ^*	a ^*	b ^*	Melt liquid level stability	The polymer color observations	% foam in polyester	The vision grading of polyester	A	82.50	-0.89	4.66	4	Yellowing	34％	4
B	79.74	-0.75	4.89	4	Yellowing	21％	4	A	82.50	-0.89	4.66	4	Yellowing	34％	4
B	79.74	-0.75	4.89	4	Yellowing	21％	4	C	78.64	-0.39	6.83	4	Pale brown look	37％	4
D	85.44	-1.45	4.07	3	Light yellow	27％	4	C	78.64	-0.39	6.83	4	Pale brown look	37％	4
D	85.44	-1.45	4.07	3	Light yellow	27％	4	E	86.19	-1.04	3.94	3	Good color: not yellowing	35％	4
F	80.92	-1.02	3.22	2	Good color: not yellowing	20％	3	E	86.19	-1.04	3.94	3	Good color: not yellowing	35％	4
F	80.92	-1.02	3.22	2	Good color: not yellowing	20％	3	G	82.10	-1.67	3.69	2	Good color: not yellowing	22％	3
H	85.74	-0.81	2.46	1	NM	NM	NM	G	82.10	-1.67	3.69	2	Good color: not yellowing	22％	3
H	85.74	-0.81	2.46	1	NM	NM	NM	I	82.51	-1.03	2.56	1	Good color: not yellowing	15％	2
J	85.54	-1.07	2.06	1	Good color: not yellowing	22％	3	I	82.51	-1.03	2.56	1	Good color: not yellowing	15％	2
J	85.54	-1.07	2.06	1	Good color: not yellowing	22％	3	K	84.54	-0.71	1.07	1	Good color: not yellowing	14％	2
L	85.03	-0.82	1.17	1	Light yellow	14％	3	K	84.54	-0.71	1.07	1	Good color: not yellowing	14％	2
L	85.03	-0.82	1.17	1	Light yellow	14％	3	M	85.02	-0.87	1.59	1	Light yellow	17％	2
N	82.49	-0.86	1.09	1	Good color: not yellowing	17％	2	M	85.02	-0.87	1.59	1	Light yellow	17％	2
N	82.49	-0.86	1.09	1	Good color: not yellowing	17％	2	O	NA	NA	NA	NA	NA	35％	NA
P	NA	NA	NA	NA	NA	9％	NA	O	NA	NA	NA	NA	NA	35％	NA

NM=does not measure

[0500] be recorded in melt liquid level stability in the table 13 based on following yardstick:

1 stable melt liquid level, the limited gas of emitting is similar to the normal polyester that excess diol wherein cooks out at leisure.
	2 compare with above 1, metastable melt liquid level but some additional space/bubbles.
3 under vacuum level unsettled melt liquid level, the foaming of severe and foaming causes high void volume (increasing the bubble of melt cumulative volume), the unsettled gas of emitting, melt liquid level springs up-only by means of the adjusting of stir speed (S.S.) or more than the liquid level of melt, have agitator to press and broken this foam prevents to overflow from flask.Too unstable so that can't amplify in proportion credibly.
	4 in vacuum level very unsettled melt liquid level, over-drastic foams and foams and causes high void volume (increasing the bubble of melt cumulative volume), the unsettled gas of emitting, melt liquid level spring up-overflow from flask and frequently melt/foam is pushed in the gas space in the vacuum system.Can not finish experiment (, can't finish) frequently greater than 50% repeated experiments round for the stability of this level.

[0501] vision that is recorded in the table 13 is graded based on following yardstick:

Grading	Explain
Grading	Explain	1	The bubble of gas seldom: as seen pass through molten polymer
2	Rare bubble: have enough bubbles to hinder and watch, but be not enough to increase sharp polymer volume by polymkeric substance	1
2		3	A lot of bubbles: the volume of polymkeric substance is subjected to aeration
4	Very close foam: the volume of polymkeric substance is subjected to the violent influence of a lot of bubbles	3

[0502] embodiment 25O and embodiment 25P are Comparative Examples.Embodiment 25O represent with the similar mode of following pilot scale embodiment prepare but contain the polyester of without phosphorus thermo-stabilizer, it has the IV of 0.54dL/g and contains 100mol% terephthalic acid residue, 43.8mol%TMCD residue and 56.2 moles of %CHDM acid residues.These polyester prepare under 290 ℃ final precision work actuator temperature as the source (Sn=216ppm) of tin catalyst by using three-2 ethyl hexanoic acid butyl tin, and have colour L ^*=60.97, b ^*=9.02, and a ^*=-0.89.Embodiment 25P represents to contain 65mol% terephthalic acid residue, 35mol% isophthalic acid residues and 100mol%1, the commodity Kelvx polymkeric substance of 4-cyclohexanedimethanol residue.

[0503] polyester of present embodiment is to prepare in the 500ml round-bottomed flask that agitator and polymkeric substance head are housed, and this polymkeric substance head allows nitrogen purging simultaneously and vacuumizes, when needs.Starting material are weighed into carry out 0.4 mole of experiment (polymer repeat unit=274 gram/moles) in the flask: the TMCD (36.8 restrain) of 0.400 mole DMT (77.6 gram), 0.224 mole CHDM (32.3 gram) and 0.256 mole and 0.112g three-2 ethyl hexanoic acid butyl tin or 0.0314g tin methide oxide compound (such as in the table 12 record), make the metallic tin that in final polymkeric substance, has about 200ppm, but therefore make improvements for other aimed concn such as 100ppm Sn.

[0504] glycol/sour ratio is 1.2/1, and wherein excessive is, and 2% CHDM and 20% excessive remainder are TMCD.Catalyzer is weighed in the flask, as solid or liquid.To be weighed in the flask as the solid Triphenyl phosphate for the amount of each experiment according to record in table 12.The tetramethyl ammonium hydroxide (TMAH) of 100ppm (0.0109g is as liquid) is used for the preparation of embodiment 25K.

[0505] make setting point and data gathering more convenient by Camile method Controlling System.In case reactant fusing, start stir and according to following in corresponding C amile sequence specified increase like that at leisure (stirring velocity).Along with the passing of experimental period, the temperature of reactor also raises gradually.

[0506] transesterify and polycondensation are carried out in same 500ml flask.The blade of agitator is moved upwards up to the top of melt with constrain foam layer in the course of processing of the polyester of embodiment 25A and embodiment 25B.Be recorded in the following table by the temperature/pressure/stir speed (S.S.) sequence of Camile software control for each embodiment.The final polymerization temperature of the experiment of present embodiment (Pz temperature) be 265 ℃ to 290 ℃ and be recorded in the table 12.

[0507] the Camile sequence of embodiment 25A-embodiment 25I

Stage	Time (minute)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature (℃)	Vacuum (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	5	245	760	50
12	30	265	760	50	11	5	245	760	50
12	30	265	760	50	13	3	265	90	50
14	110	290	90	50	13	3	265	90	50
14	110	290	90	50	15	5	290	6	25
16	110	290	6	25	15	5	290	6	25
16	110	290	6	25	17	2	290	400	0
18	1	300	760	0	17	2	290	400	0

[0508] the Camile sequence of embodiment 25J-embodiment 25L

Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	5	25
16	110	255	5	25	15	3	255	5	25
16	110	255	5	25	17	3	265	1	25
18	110	265	1	25	17	3	265	1	25
18	110	265	1	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

[0509] the Camile sequence of embodiment 25M

The sequence of viscosity limitation, rough vacuum

Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	5	25
16	110	255	5	25	15	3	255	5	25
16	110	255	5	25	17	3	265	0.2	25
18	110	265	0.2	25	17	3	265	0.2	25
18	110	265	0.2	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

[0510] the Camile sequence of embodiment 25N

The sequence of viscosity limitation, rough vacuum

Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	01	200	760	100	3	2	200	760	25
4	01	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	3	25
16	110	255	3	25	15	3	255	3	25
16	110	255	3	25	17	3	265	0.2	25
18	110	265	0.2	25	17	3	265	0.2	25
18	110	265	0.2	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

Embodiment 26

[0511] present embodiment illustrates by using the processing condition different with embodiment 25, comprises the preparation method of the polyester of at least a thermo-stabilizer, its reaction product and composition thereof, obtains the improvement stability of polyester fondant in the course of processing.

[0512] various polyester are as described below from 100mol%DMT, CHDM and TMCD preparation.The mol% that is used for the TMCD of present embodiment experiment is recorded in following table 14, and wherein the glycol surplus is CHDM.DMT, CHDM and TMCD have the source identical with embodiment 25.Catalyzer is cacodyl oxide base tin (Strem Chemical Co., Batch B4058112), three-2 ethyl hexanoic acid butyl tin (Aldrich, Batch 06423CD, or Arkema) or dibutyltin oxide (Arkema).Thermo-stabilizer is a Triphenyl phosphate, also with embodiment 25 in identical source.Unless explanation is below arranged in addition, the source of phosphorus is that the remainder with polyester reagent adds in advance.The cis/trans ratios of CHDM as previously discussed, and the cis/trans ratios of TMCD is recorded in the table 14.The polyester of embodiment 26A and embodiment 26E is not to use the TPP preparation.

Table 14

The composition of the polyester of embodiment 26 and logarithmic viscosity number

Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)
Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)	A	0.548	46.3	50.1	190 ³	Do not have	*	290
B	0.696	45.3	49.3	193 ²	10/9	21.4	275	A	0.548	46.3	50.1	190 ³	Do not have	*	290
B	0.696	45.3	49.3	193 ²	10/9	21.4	275	C	0.597	45.1	50.4	199 ²	20/18	11.1	275
D	0.547	45.6	50.4	195 ²	30/27	7.2	275	C	0.597	45.1	50.4	199 ²	20/18	11.1	275
D	0.547	45.6	50.4	195 ²	30/27	7.2	275	E	0.714	45.4	49.9	198 ²	Do not have	*	265
F	0.731	44.5	48.0	188 ²	30/25	7.5	265	E	0.714	45.4	49.9	198 ²	Do not have	*	265
F	0.731	44.5	48.0	188 ²	30/25	7.5	265	G	0.727	44.7	48.5	203 ²	30/26	7.8	265
H	0.645	44.0	51.0	55 ²	7.5/8	6.9	265	G	0.727	44.7	48.5	203 ²	30/26	7.8	265
H	0.645	44.0	51.0	55 ²	7.5/8	6.9	265	I	0.605	43.3	48.6	55 ²	7.5/8	6.9	265
J	0.711	46.1	48.6	196 ²	20/17	11.5	275	I	0.605	43.3	48.6	55 ²	7.5/8	6.9	265
J	0.711	46.1	48.6	196 ²	20/17	11.5	275	K	0.721	45.8	48.8	193 ²	20/17	11.4	275

1 three-2 ethyl hexanoic acid butyl tin is as the source of tin

2 cacodyl oxide base tin are as the source of tin

3 dibutyltin oxides are as the source of tin

[0513] data show in the table 15, and the stability of polymer melt can be by improving processing condition, wait as the final polymerization temperature of following report, the vacuum rate that produces in reactor, time under vacuum to strengthen.Melt liquid level stability in table 15 and vision grading are based on disclosed yardstick among the embodiment 25.

Table 15

The performance of the polyester of embodiment 26

Embodiment	L ^*	a ^*	b ^*	Melt liquid level stability	The polymer color observations	% foam in the polyester	The vision grading of polyester
Embodiment	L ^*	a ^*	b ^*	Melt liquid level stability	The polymer color observations	% foam in the polyester	The vision grading of polyester	A	83.55	-0.93	2.44	2	Light yellow	30％	4
B	84.39	-1.48	3.89	1	Good color: not yellowing	29％	4	A	83.55	-0.93	2.44	2	Light yellow	30％	4
B	84.39	-1.48	3.89	1	Good color: not yellowing	29％	4	C	84.46	-0.98	1.82	1	Light yellow	21％	2
D	86.30	-0.75	1.27	1	Good color: not yellowing	17％	2	C	84.46	-0.98	1.82	1	Light yellow	21％	2
D	86.30	-0.75	1.27	1	Good color: not yellowing	17％	2	E	85.60	-1.20	2.68	3	Yellow	38％	4
F	83.88	-0.97	1.64	1	Light yellow	12％	1	E	85.60	-1.20	2.68	3	Yellow	38％	4
F	83.88	-0.97	1.64	1	Light yellow	12％	1	G	85.76	-0.92	2.03	1	Light yellow	12％	2
H	84.40	-098	1.61	1	Good color: not yellowing	NM	1	G	85.76	-0.92	2.03	1	Light yellow	12％	2
H	84.40	-098	1.61	1	Good color: not yellowing	NM	1	I	84.88	-0.63	0.99	1	Light yellow	11％	1
J	85.01	-1.02	1.77	1	Light yellow	18％	3	I	84.88	-0.63	0.99	1	Light yellow	11％	1
J	85.01	-1.02	1.77	1	Light yellow	18％	3	K	84.13	-0.93	1.56	1	Light yellow	25％	4

NM=does not measure

Embodiment 26A

[0514] in the 500ml round-bottomed flask, adds 0.4 mole DMT (77.6 gram), 0.224 mole CHDM (32.3 gram), 0.256 mole TMCD (36.8 gram) and 0.0460 dibutyltin oxide that restrains.This flask is equipped with the stainless steel agitator and allows nitrogen purging simultaneously and the polymkeric substance head of vacuum ability.Flask immersed in 200 ℃ the Belmont metal bath and stirring under the 25RPM till the content fusing.Stir speed (S.S.) is brought up to 200RPM and these conditions were kept 3 hours 15 minutes.Temperature is brought up to 220 ℃ and these conditions were kept other 30 minutes.Temperature was brought up to 290 ℃ through 20 minutes.After reaching 290 ℃, with pressure through be reduced to 0.3 setting point (SP) in 15 minutes from normal atmosphere.Along with viscosity increases, stir speed (S.S.) is reduced to minimum 15RPM.Measured minimum vacuum tightness reading is that 0.70 (even SP is 0.3) and the total time under vacuum are 30 minutes.

[0515] remainder of the polyester of present embodiment is to prepare in the 500ml round-bottomed flask that agitator and polymkeric substance head are housed, and this polymkeric substance head allows nitrogen purging simultaneously and vacuumizes, when needs.Starting material are weighed into carry out 0.4 mole of experiment (polymer repeat unit=274 gram/moles) in the flask: the TMCD (36.8 restrain) of 0.400 mole DMT (77.6 gram), 0.224 mole CHDM (32.3 gram) and 0.256 mole and the dibutyltin oxide of 0.112g three-2 ethyl hexanoic acid butyl tin, 0.0314g cacodyl oxide base tin or 0.0460g (such as in the table 14 record).These numerical value show as the aimed concn of 200ppm Sn in final polymkeric substance and therefore regulate for other aimed concn.The actual tin concentration of each polyester is recorded in the table 14 in the present embodiment.

[0516] glycol/sour ratio in only two experiments in the present embodiment is 1.2/1, and wherein excessive is that 2%CHDM and 20% excessive remainder are TMCD.The glycol of embodiment 26H/sour ratio is 1.1/1, and that wherein excessive is TMCD.The glycol of embodiment 26I/sour ratio is 1.05/1, and that wherein excessive is TMCD.Catalyzer is weighed in the flask, as solid or liquid.Amount according to record in table 14 will be weighed in the flask as the solid Triphenyl phosphate.TPP in embodiment 26K adds from methanol solution subsequently.

[0517] make setting point and data gathering more convenient by Camile method Controlling System.In case reactant fusing, start stir and according to following in corresponding C amile sequence specified increase like that at leisure (stirring velocity).Along with the passing of experimental period, the temperature of reactor also raises gradually.

[0518] transesterify and polycondensation are carried out in same 500ml flask.Be recorded in the following table by the temperature/pressure/stir speed (S.S.) sequence of Camile software control for each embodiment.The final polymerization temperature of the experiment of present embodiment (Pz temperature) be 265 ℃ to 290 ℃ and be recorded in the table 14.

[0519] the Camile sequence of embodiment 26B-embodiment 26D

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	32	250	375	50
12	30	255	375	50	11	32	250	375	50
12	30	255	375	50	13	3	255	50	50
14	30	260	50	50	13	3	255	50	50
14	30	260	50	50	15	3	265	15	25
16	110	265	15	25	15	3	265	15	25
16	110	265	15	25	17	3	270	2	25
18	110	275	2	25	17	3	270	2	25
18	110	275	2	25	19	2	275	400	0
20	1	275	760	0	19	2	275	400	0

[0520] the Camile sequence of embodiment 26E

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	5	25
16	110	255	5	25	15	3	255	5	25
16	110	255	5	25	17	3	265	1	25
18	110	265	1	25	17	3	265	1	25
18	110	265	1	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

[0521] the Camile sequence of embodiment 26F and embodiment 26G

The sequence of viscosity limitation, rough vacuum

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	5	25
16	110	255	5	25	15	3	255	5	25
16	110	255	5	25	17	3	265	0.2	25
18	110	265	0.2	25	17	3	265	0.2	25
18	110	265	0.2	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

[0522] the Camile sequence of embodiment 26H and embodiment 26I

The sequence of viscosity limitation, rough vacuum

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	255	3	25
16	110	255	3	25	15	3	255	3	25
16	110	255	3	25	17	3	265	1	25
18	110	265	1	25	17	3	265	1	25
18	110	265	1	25	19	2	265	400	0
20	1	265	760	0	19	2	265	400	0

[0523] the Camile sequence of embodiment 26J and embodiment 26K

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	5	245	760	50	9	120	210	760	200
10	5	245	760	50	11	3	245	375	50
12	30	245	375	50	11	3	245	375	50
12	30	245	375	50	13	3	250	20	50
14	30	250	20	50	13	3	250	20	50
14	30	250	20	50	15	3	260	5	25
16	110	260	5	25	15	3	260	5	25
16	110	260	5	25	17	3	275	1	25
18	110	275	1	25	17	3	275	1	25
18	110	275	1	25	19	2	275	400	0
20	1	275	760	0	19	2	275	400	0

Embodiment 27

[0524] present embodiment illustrates and adopts the different thermo-stabilizers to prepare the method for polyester and shown their influences for the stability of polyester fondant in the course of processing.

[0525] various polyester CHDM and TMCD preparation from 100mol%DMT and different concns as described below.The mol% that is used for the TMCD of present embodiment experiment is recorded in following table 16, and wherein the glycol surplus is CHDM.DMT, CHDM and TMCD have the source identical with embodiment 25.Catalyzer is cacodyl oxide base tin (Strem Chemical Co., Batch B4058112) or three-2 ethyl hexanoic acid butyl tin (Aldrich, Batch 06423CD).Merpol A (the octanol phosphate mixture of DuPont) is specified and be selected to thermo-stabilizer in table 16, triethyl phosphate (Aldrich), Irgafos 168 (three (2, the 4-di-tert-butyl-phenyl) phosphoric acid ester, Ciba SpecialtyChemicals), Doverphos 9228 (CAS#154862-43-8, two (2, the 4-dicumylphenyl) pentaerythritol diphosphites, Dover), Weston 619g (CAS#85190-63-2,2-propyl alcohol, 1,1 '; 1 "-nitrilo three (nitrilotris)-, mixture contains 3, two (the octadecane oxygen bases)-2 of 9-, 4,8,10-four oxa-s-3,9-two phospha spiral shell [5.5] undecanes, GE SC), triphenylphosphine oxidation thing (Aldrich), Triphenyl phosphate (Aldrich or FERRO), NaH ₂PO ₄(Aldrich), Zn ₃(PO ₄) ₂(Aldrich) and H ₃PO ₄(Aldrich).Unless explanation is arranged in table 16 in addition, the source of phosphorus is that the remainder with polyester reagent adds in advance.The cis/trans ratios of CHDM as previously discussed, and the cis/trans ratios of TMCD is recorded in the table 16.

Table 16

The composition of the polyester of embodiment 27 and logarithmic viscosity number

Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)
Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory/measurement	The actual wt ratio of Sn/P	Final Pz temperature (℃)	A	0.564	45.7	49.7	211 ²	28/26	8.1	265
B	0.167	29.2	58.2	218 ²	28/39	5.6	265	A	0.564	45.7	49.7	211 ²	28/26	8.1	265
B	0.167	29.2	58.2	218 ²	28/39	5.6	265	C	0.647	45.2	49.2	195 ²	20/19	10.3	265
D	0.674	46.3	48.7	196 ²	20/18	10.9	265	C	0.647	45.2	49.2	195 ²	20/19	10.3	265
D	0.674	46.3	48.7	196 ²	20/18	10.9	265	E	0.700	45.6	49.4	195 ²	20/0	*	265
F	0.738	45.9	49.0	214 ²	20/8	26.8	265	E	0.700	45.6	49.4	195 ²	20/0	*	265
F	0.738	45.9	49.0	214 ²	20/8	26.8	265	G	0.672	46.4	49.7	192 ²	20/11	17.5	265
H	0.714	46.0	48.5	189 ²	20/7	27.0	265	G	0.672	46.4	49.7	192 ²	20/11	17.5	265
H	0.714	46.0	48.5	189 ²	20/7	27.0	265	I	0.73	42.3	45.1	212 ¹	0	*	265
J	0.58	44.4	44.5	209 ¹	28/27	7.7	265	I	0.73	42.3	45.1	212 ¹	0	*	265
J	0.58	44.4	44.5	209 ¹	28/27	7.7	265	K	0.53	43.4	45.0	213 ¹	28/28	7.6	265
L	0.69	44.3	44.4	209 ¹	28/20	10.5	265	K	0.53	43.4	45.0	213 ¹	28/28	7.6	265
L	0.69	44.3	44.4	209 ¹	28/20	10.5	265	M	0.61	43.7	45.4	211 ¹	28/25	8.4	265
N	0.76	43.9	44.4	200 ¹	28/20	10.0	265	M	0.61	43.7	45.4	211 ¹	28/25	8.4	265
N	0.76	43.9	44.4	200 ¹	28/20	10.0	265	O	0.66	44.6	44.3	58 ¹	0	*	265
P	0.6	42.4	44.7	60 ¹	7/7	8.6	265	O	0.66	44.6	44.3	58 ¹	0	*	265
P	0.6	42.4	44.7	60 ¹	7/7	8.6	265	Q	0.5	42.9	45.4	57 ¹	7/7	8.1	265
R	0.51	43.8	45.1	52 ¹	200/55 ⁴	0.9	265	Q	0.5	42.9	45.4	57 ¹	7/7	8.1	265
R	0.51	43.8	45.1	52 ¹	200/55 ⁴	0.9	265	S	0.64	44.0	44.4	58 ¹	200/71 ⁴	0.8	265

1 three-2 ethyl hexanoic acid butyl tin is as the source of tin

2 cacodyl oxide base tin are as the source of tin

3 dibutyltin oxides are as the source of tin

4 existence owing to insoluble substance, polymkeric substance is muddy

[0526] data presentation in the table 17 stability of polymer melt when adopting different phosphorus source as thermo-stabilizer.Though embodiment 27B has exceeded the scope of Original submission claim with regard to mol%TMCD, it is included in herein and adopts phosphoric acid as thermo-stabilizer to show.Data presentation, phosphoric acid ester provides stable melt and acceptable polyester product with the phosphorus compound that can be hydrolyzed into phosphoric acid ester.Melt liquid level stability in table 17 and vision grading are based on disclosed yardstick among the embodiment 25.

Table 17

The performance of the polyester of embodiment 27

Embodiment	L ^*	a ^*	b ^*	The phosphorus source	Melt liquid level stability	The polymer color observations	% foam in the polyester	The vision grading of polyester
Embodiment	L ^*	a ^*	b ^*	The phosphorus source	Melt liquid level stability	The polymer color observations	% foam in the polyester	The vision grading of polyester	A	83.87	-1.09	1.61	MerpolA	1	NM	NM	NM
B	NM	NM	NM	H ₃PO ₄	1	Good color: not yellowing	7％	1	A	83.87	-1.09	1.61	MerpolA	1	NM	NM	NM
B	NM	NM	NM	H ₃PO ₄	1	Good color: not yellowing	7％	1	C	84.84	-0.94	1.40	MerpolA	1	Good color: not yellowing	22％	3
D	85.86	-0.69	1.07	After EE, add MerpolA	1	Light yellow	21％	3	C	84.84	-0.94	1.40	MerpolA	1	Good color: not yellowing	22％	3
D	85.86	-0.69	1.07	After EE, add MerpolA	1	Light yellow	21％	3	E	8377	-1.12	1.91	The tricresyl phosphate ethyl ester	2	Light yellow	25％	4
F	84.05	-2.06	8.66	The tricresyl phosphate ethyl ester	2	General pale brown look	22％	4	E	8377	-1.12	1.91	The tricresyl phosphate ethyl ester	2	Light yellow	25％	4
F	84.05	-2.06	8.66	The tricresyl phosphate ethyl ester	2	General pale brown look	22％	4	G	7763	-0.82	3.33	Irgafos 168	3	NM	NM	NM
H	78.68	-0.83	3.34	After EE, add Irgafos 168	3	General pale brown look	24％	4	G	7763	-0.82	3.33	Irgafos 168	3	NM	NM	NM
H	78.68	-0.83	3.34	After EE, add Irgafos 168	3	General pale brown look	24％	4	I	NM	NM	NM	Do not have	NN	Light yellow	26％	4
J	NM	NM	NM	Doverphos 9228	NN	Good color: not yellowing	21％	3	I	NM	NM	NM	Do not have	NN	Light yellow	26％	4
J	NM	NM	NM	Doverphos 9228	NN	Good color: not yellowing	21％	3	K	NM	NM	NM	Doverphos 9228	NN	NM	NM	NM
L	NM	NM	NM	Weston 619g	NN	Good color: not yellowing	21％	4	K	NM	NM	NM	Doverphos 9228	NN	NM	NM	NM
L	NM	NM	NM	Weston 619g	NN	Good color: not yellowing	21％	4	M	NM	NM	NM	Triphenyl phosphate	NN	Light yellow	14％	2
N	NM	NM	NM	Triphenylphosphine oxidation thing	NN	Light yellow	23％	3	M	NM	NM	NM	Triphenyl phosphate	NN	Light yellow	14％	2
N	NM	NM	NM	Triphenylphosphine oxidation thing	NN	Light yellow	23％	3	O	NM	NM	NM	Do not have	NN	Light yellow	19％	2
P	NM	NM	NM	Triphenyl phosphate	NN	NM	NM	NM	O	NM	NM	NM	Do not have	NN	Light yellow	19％	2
P	NM	NM	NM	Triphenyl phosphate	NN	NM	NM	NM	Q	NM	NM	NM	Triphenyl phosphate	NN	Good color: not yellowing	10％	1
R	NM	NM	NM	NaH ₂PO ₄	NN	Good color: not yellowing	17％	1	Q	NM	NM	NM	Triphenyl phosphate	NN	Good color: not yellowing	10％	1
R	NM	NM	NM	NaH ₂PO ₄	NN	Good color: not yellowing	17％	1	S	NM	NM	NM	Zn ₃(PO ₄) ₂	NN	Good color: not yellowing	16％	2

The EE=transesterify; NM=does not measure; NN=is record not

The sample of embodiment R is muddy, so the vision grading may be influenced

Embodiment 27A-embodiment 27H

[0527] these polyester manufacture are as follows.With 77.6g (0.4mol) dimethyl terephthalate (DMT), 32.3g (0.224mol) 1,4-cyclohexanedimethanol, 36.8g (0.256mol) 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol add in the 500ml flask that nitrogen ingress pipe, metal agitator and short distillation column are housed.Catalyzer also is added in the reaction flask.The amount and the type of catalyzer are at length listed in the table 16.Phosphorus compound also is added in the reaction flask.The theory and the measuring vol of the phosphorus compound of each experiment are listed in the table 16 in detail in the present embodiment.Flask is placed Wood (Wood) metal bath that is heated to 200 ℃.For each experiment temperature/pressure/the stir speed (S.S.) sequence is by the Camile software control and be recorded in down.In some cases, (embodiment 27D and embodiment 27H) adds phosphorus additive after transesterify under the situation of note.This is corresponding to the end in stage 9 in corresponding C amile sequence.

Embodiment 27I-embodiment 27S

[0528] these polyester manufacture are as follows.With 77.6g (0.4mol) dimethyl terephthalate (DMT), 33.31g (0.231mol) 1,4-cyclohexanedimethanol, 35.91g (0.249mol) 2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol add in the 500ml flask that nitrogen ingress pipe, metal agitator and short distillation column are housed.Catalyzer also is added in the reaction flask.The amount and the type of catalyzer are at length listed in the table 16.The source of phosphorus is weighed in the flask according to the amount of listing in the table 16, in this table, comprises the theory of each experiment and the amount of the phosphorus compound of measurement.Flask is placed the Wood metal bath that is heated to 200 ℃.For each embodiment temperature/pressure/the stir speed (S.S.) sequence is by the Camile software control and be recorded in down.

[0529] glycol of whole experiments in the present embodiment/sour ratio is 1.2/1, and wherein excessive is that 2%CHDM and 20% excessive remainder are TMCD.Catalyzer is weighed in the flask as solid or liquid.

[0530] make setting point and data gathering more convenient by Camile method Controlling System.In case reactant fusing, start stir and according to following in corresponding C amile sequence specified increase like that at leisure (stirring velocity).Along with the passing of experimental period, the temperature of reactor also raises gradually.

[0531] is recorded in the following table by the temperature/pressure/stir speed (S.S.) of Camile software control for each embodiment.The final polymerization temperature of the experiment of present embodiment (Pz temperature) is 265 ℃.

[0532] the Camile sequence of embodiment 27A and embodiment 27B

The sequence of viscosity limitation

Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)
Stage	Time (minute)	Temperature, ℃	Vacuum tightness (holder)	Stir speed (S.S.) (RPM)	1	3	200	760	0
2	0.1	200	760	25	1	3	200	760	0
2	0.1	200	760	25	3	2	200	760	25
4	0.1	200	760	100	3	2	200	760	25
4	0.1	200	760	100	5	1	200	760	100
6	0.1	200	760	200	5	1	200	760	100
6	0.1	200	760	200	7	90	200	760	200
8	0.1	210	760	200	7	90	200	760	200
8	0.1	210	760	200	9	120	210	760	200
10	0.1	220	760	200	9	120	210	760	200
10	0.1	220	760	200	11	30	220	760	200
12	5	245	760	50	11	30	220	760	200
12	5	245	760	50	13	3	245	375	50
14	30	245	375	50	13	3	245	375	50
14	30	245	375	50	15	3	250	20	50
16	30	250	20	50	15	3	250	20	50
16	30	250	20	50	17	3	255	3	25
18	110	255	3	25	17	3	255	3	25
18	110	255	3	25	19	3	265	1	25
20	110	265	1	25	19	3	265	1	25

[0533] the Camile sequence of embodiment 27C-embodiment 27S

The sequence of viscosity limitation, rough vacuum

Embodiment 28

[0534] present embodiment illustrates the preparation method of polyester on the pilot plant scale who comprises at least a thermo-stabilizer, its reaction product and composition thereof, obtains the improvement stability of polyester fondant in the course of processing.

[0535] various polyester are as described below from 100mol%DMT, CHDM and TMCD preparation.The mol% that is used for the TMCD of present embodiment experiment is listed in the table below 18, and wherein the glycol surplus is CHDM.DMT, CHDM and TMCD have the source identical with embodiment 25.Catalyzer is cacodyl oxide base tin (Strem Chemical Co., Batch B4058112) or three-2 ethyl hexanoic acid butyl tin (Aldrich, Batch 06423CD).Thermo-stabilizer be Triphenyl phosphate (TPP) (Aldrich).Unless explanation is below arranged in addition, the source of phosphorus is that the remainder with polyester reagent adds in advance.The cis/trans ratios of CHDM as previously discussed, and the cis/trans ratios of TMCD is recorded in the table 18.

Table 18

The composition of the polyester of embodiment 28 and logarithmic viscosity number

Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory	L ^*	a ^*	b ^*
Embodiment	Melt IV (dL/g)	TMCD (mol％)	TMCD % cis	Sn (ppm)	P (ppm) theory	L ^*	a ^*	b ^*	A	0.553	46.1	45.8	228 ²	300	80.50	-1.51	4.27
B	0.620	46.0	46.0	204 ¹	100	83.42	-1.18	4.92	A	0.553	46.1	45.8	228 ²	300	80.50	-1.51	4.27
B	0.620	46.0	46.0	204 ¹	100	83.42	-1.18	4.92	C	0.613	45.1	46.3	193 ¹	100	77.60	-1.80	4.85
D	0.624	45.4	46.2	209 ²	100	79.69	-1.71	6.45	C	0.613	45.1	46.3	193 ¹	100	77.60	-1.80	4.85

1 three-2 ethyl hexanoic acid butyl tin is as the source of adopting of tin

2 cacodyl oxide base tin are as the source of tin

Embodiment 28A

[0536] 84.96 pound of (198.83gram-mol) dimethyl terephthalate (DMT), 35.38 pounds of (111.54gram-mol) 1,4-cyclohexanedimethanol, 40.30 pounds of (127.06gram-mol) 2,2,4,4-tetramethyl--1,3-cyclobutanediol react in the presence of as the cacodyl oxide base tin of the 200ppm of tin catalyst and 300ppm Triphenyl phosphate (16.35 gram) together.Be reflected in 74 gallons of stainless steel pressurizing vessels that condensation tower, vacuum system and HELICONE type agitator are housed and under nitrogen purging, carry out.Agitator turns round with 25RPM, and reaction mixture temperature is brought up to 250 ℃ and pressure and brought up to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.This pressure is reduced to 0psig with the speed of 3psig/min then.Agitator speed is lowered to 15RPM then, and the temperature of reaction mixture is brought up to 270 ℃ and pressure then and is reduced to≤1-mm Hg.Reaction mixture 270 ℃ and≤kept 3.75 hours under the pressure of 1mm Hg.The pressure of container uses nitrogen to bring up to 1 normal atmosphere then.Molten polymer uses extrusion die to extrude from pressurizing vessel then.The polymkeric substance tow of extruding is stretched and cools off by cooling bath, after this with the tow pelletizing.The polymkeric substance that is cut into pellet has 0.553 logarithmic viscosity number.NMR analysis revealed, polymkeric substance be by 53.9mol%1,4-cyclohexanedimethanol part and 46.1mol%2, and 2,4,4-tetramethyl--1,3-tetramethylene glycol moiety is formed.Polymkeric substance has following colour: L ^*=80.50, a ^*=-1.51, and b ^*=4.27.

[0537] embodiment 28B-embodiment 28D has disclosed composition in table 17 according to preparing with the similar mode of embodiment 28A.

[0538] embodiment 28E represents to have the IV of 0.73dL/g from the PCTGEastar DN001 of Eastman Chemical Company acquisition, and nominal consists of 100mol% terephthalic acid residue, 62mol%CHDM residue and 38mol% glycol residue.Embodiment 28F represents that nominal consists of 100mol% dihydroxyphenyl propane residue and 100mol% diphenyl carbonate residue from the polycarbonate Makrolon 2608 of Bayer acquisition.Embodiment 28G represents Eastman ChemicalCompany polyester, and nominal consists of 100mol% terephthalic acid residue, 55mol%CHDM residue and 45mol%TMCD residue.Embodiment 28H represents that nominal consists of 100mol% terephthalic acid, 31mol% cyclohexanedimethanol (CHDM) and 69mol% ethylene glycol from the PETG Eastar 6763 of Eastman ChemicalCompany acquisition.

Embodiment 28I

[0539] polyester of embodiment 28I is the blend of 10 kinds of different polyester, prepares by following mode separately.84.96 pound (198.83gram-mol) dimethyl terephthalate (DMT) is in the presence of the tin catalyst (being three-thylhexoic acid butyl tin) of 200ppm and 50.45-51.46 pound (159.06-162.24gram-mol, depend on batch of material) 1,4-cyclohexanedimethanol and 24.22-31.53 pound (76.36-99.41gram-mol, also depend on batch of material) 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol reacts.Reaction is to carry out under nitrogen purging in 74 gallons of stainless steel pressurizing vessels that condensation tower, vacuum system and HELICONE type agitator are housed, and obtains glycol/dimethyl terephthalate (DMT) mol ratio of 1.2/1-1.3/1.Agitator turns round with 25RPM, and reaction mixture temperature is brought up to 250 ℃ and pressure and brought up to 20psig.Reaction mixture kept 2 hours under 250 ℃ and 20psig pressure.Pressure is reduced to 0psig with the speed of 3psig/min then.Agitator speed is reduced to 15RPM then, and the temperature of reaction mixture is brought up to 260-270 ℃ and pressure then and is reduced to 90mmHg.Reaction mixture kept 1 hour under 260-270 ℃ and 90-mm Hg pressure.The temperature of reaction mixture is brought up to 275-290 ℃ and pressure then and is reduced to≤1mm Hg.Reaction mixture 275-290 ℃ and≤keep 1.5-3 hour to finish polycondensation phase under the 1mm Hg.The pressure of pressurizing vessel uses nitrogen to bring up to 1 normal atmosphere then.Molten polymer is expressed in the cooling bath from pressurizing vessel then.The refrigerative extruded polymer is ground the screen cloth by 6-mm.

[0540] uses ten independent batch of materials of said procedure preparation.Following table comprises for 10 NMR that batch of material obtained compositions, IV value and colours.Final polyester blend has the IV of 0.63dL/g, the target of 100mol% terephthalic acid residue and 20mol%TMCD residue and 80mol%CHDM residue.

[0541] plate (4 inches * 4 inches * 1/8 inch thickness) is from the polyester manufacture of table 18 in Toyo 110 injection press.Add to the pellet of each polyester in the press and be heated to the temperature of record in the table 19.Molten polymer residence time in machine barrel before injection also is recorded in the table 19.In case this part is fully cooling, and it is carried out visual analysis and is recorded in the splay mark that produces in the injection moulding process.

[0542] data presentation in the table 19 condition of moulding influence that splay mark in the injection molding plates of being made by the polyester in the table 18 is produced.

Table 19

Splay mark in the moulding part that the polyester of embodiment 28 is made produces

Splay mark grading: do not have (0) slight (1), medium (2), serious (3); NA=does not obtain

[0543] data presentation in the table 20 quality of the film made by the polyester in the table 18.

[0544] polymkeric substance is by using general spiro rod 1.5 " extrude on the Killion forcing machine.Polymkeric substance is extruded under the temperature of 572 (300 ℃) and 527 (275 ℃).Following forcing machine condition is used for each polymkeric substance extruding under 572:

Sample	Zone temperatures	Die head temperature	The Die-head connecting sleeve temperature	The clamping ring temperature	Melt temperature	Pressure (PSI)	Screw speed (RPM)	Chill roll speed (RPM)
Sample	Zone temperatures	Die head temperature	The Die-head connecting sleeve temperature	The clamping ring temperature	Melt temperature	Pressure (PSI)	Screw speed (RPM)	Chill roll speed (RPM)	1	572	572	572	572	612	1200	70	4.3
2	572	572	572	572	619	1450	35	2.2	1	572	572	572	572	612	1200	70	4.3
2	572	572	572	572	619	1450	35	2.2	3	572	572	572	572	618	2500	105	7.2

[0545] following forcing machine condition is used for each polymkeric substance extruding under 527:

Sample	Zone temperatures	Die head temperature	The Die-head connecting sleeve temperature	The clamping ring temperature	Melt temperature	Pressure (PSI)	Screw speed (RPM)	Chill roll speed (RPM)
Sample	Zone temperatures	Die head temperature	The Die-head connecting sleeve temperature	The clamping ring temperature	Melt temperature	Pressure (PSI)	Screw speed (RPM)	Chill roll speed (RPM)	1	527	527	527	527	569	1600	70	42
2	527	527	527	527	565	900	35	2.3	1	527	527	527	527	569	1600	70	42
2	527	527	527	527	565	900	35	2.3	3	527	527	527	527	571	2200	105	7.2

Table 20

The quality of the film that the polyester of embodiment 28 is made

The grading outline	Grading
The grading outline	Grading	Good film quality; Do not observe the visible bubble when leaving die head or in melt material ridge: good film is difficult in and visually detects bubble.	1
Good film quality; The accidental bubble of observing when leaving die head; Bubble in film visually detects easily but is rare.	2		1
	2	Medium film quality; See bubble when leaving die lip easily and in finished film clearly.	3
The film quality of non-constant; Tangible bubble in melt material ridge and when leaving die lip; The color of non-constant.	4		3

[0546] contrast of the data from above related work embodiment is clearly visible, with regard to regard at least a in the middle of foaming in polyester manufacture and the system of processing, splay mark, color form, foam, emit gas and unsettled melt liquid level, the polyester that polyester of the present invention is better than being purchased.

[0547] the present invention describes in detail with reference to embodiment disclosed herein, but should be appreciated that, can carry out changes and improvements within the spirit and scope of the present invention.

Claims

1. polymer blend comprises at least a polyester, and this polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%;

Wherein total mol% of dicarboxylic acid component be 100mol% and

Total mol% of diol component is 100mol%;

Wherein said polyester has 85-130 ℃ Tg.

2. the polymer blend of claim 1, wherein said logarithmic viscosity number is that 0.35-is less than 1.0dL/g.

3. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.35-0.80dL/g.

4. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.50-0.75dL/g.

5. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.6-0.75dL/g.

6. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.60-0.72dL/g.

7. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.65-0.75dL/g.

8. the polymer blend of claim 1, wherein said logarithmic viscosity number is 0.65-0.72dL/g.

9. the polymer blend of claim 1, wherein said diol component comprises 2,2,4 of 10-28mol%, 4-tetramethyl--1, the cyclohexanedimethanol residue of 3-cyclobutanediol residue and 72-90mol%.

10. the polymer blend of claim 1, wherein said diol component comprises 2,2,4 of 10-25mol%, 4-tetramethyl--1, the cyclohexanedimethanol residue of 3-cyclobutanediol residue and 75-90mol%.

11. the polymer blend of claim 1, the diol component of wherein said polyester comprises 2,2,4 of 15-28mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 72-85mol%.

12. the polymer blend of claim 1, the diol component of wherein said polyester comprises 2,2,4 of 17-28mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 72-83mol%.

13. the polymer blend of claim 1, the diol component of wherein said polyester comprises 2,2,4 of 20-30mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 70-80mol%.

14. the polymer blend of claim 1, the diol component of wherein said polyester comprises 2,2,4 of 20-26mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 35-60mol%.

15. the polymer blend of claim 1, wherein said diol component comprises 2,2,4 of 17-25mol%, 4-tetramethyl--1, the cyclohexanedimethanol residue of 3-cyclobutanediol residue and 75-83mol%.

The polymer blend of 16 claims 6, the diol component of wherein said polyester comprises 2,2,4 of 15-25mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 75-85mol%.

17. the polymer blend of claim 6, the diol component of wherein said polyester comprises 2,2,4 of 20-30mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 70-80mol%.

18. the polymer blend of claim 1, wherein said polyester has 90-115 ℃ Tg.

19. the polymer blend of claim 1, wherein said polyester has 85-115 ℃ Tg.

20. the polymer blend of claim 1, wherein said polyester has 95-115 ℃ Tg.

21. the polymer blend of claim 1, wherein said polyester has 100-125 ℃ Tg.

22. the polymer blend of claim 1, wherein said polyester has 100-120 ℃ Tg.

23. the polymer blend of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 80-100mol%.

24. the polymer blend of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 90-100mol%.

25. the polymer blend of claim 1, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 95-100mol%.

26. the polymer blend of claim 25, wherein the dicarboxylic acid component comprises the terephthalic acid residue of 99-100mol%.

27. the polymer blend of claim 1, wherein said polyester comprises 1, ammediol residue, 1,4-butyleneglycol residue or its mixture.

28. the polymer blend of claim 27, wherein said polyester comprises 1 of 0.01-25mol%, ammediol residue, 1,4-butyleneglycol residue or its mixture.

29. the polymer blend of claim 1, wherein said polyester comprises glycol residue.

30. the polymer blend of claim 1, wherein said polyester comprises the glycol residue of 0.01-15mol%.

31. the polymer blend of claim 1, wherein said polyester comprises the glycol residue of 0.01-10mol%.

32. the polymer blend of claim 1 is wherein said 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is for comprising 30-70mol% cis-2,2,4,4-tetramethyl--1, and 3-cyclobutanediol and 70-30mol% trans-2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol.

The polymer blend of 33 claims 32, wherein said 2,2,4,4-tetramethyl--1, the 3-cyclobutanediol is for comprising 40-60mol% cis-2,2,4,4-tetramethyl--1, and 3-cyclobutanediol and 60-40mol% trans-2,2,4,4-tetramethyl--1, the mixture of 3-cyclobutanediol.

34. the polymer blend of claim 1, wherein said polymer blend comprises at least a polymkeric substance, and this polymkeric substance is selected from following at least a: polyetherimide; Polyphenylene oxide; The polyphenyl ether/styrene blend; Polystyrene resin; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ether); Polycarbonate; The polyester that is different from the polyester of claim 1; Polysulfones; Polysulfones ether; With poly-(ether-ketone).

35. the polymer blend of claim 1, wherein said polymer blend comprises at least a polycarbonate.

36. the polymer blend of claim 1, wherein said polyester comprises the residue of at least a branching agent.

37. the polymer blend of claim 36, wherein said polyester comprises the residue of at least a branching agent with the amount of 0.01-10wt%, based on total molar percentage of described diacid or diol residue.

38. the polymer blend of claim 1, the melt viscosity of wherein said polyester are measured with 1 radian per second in 290 ℃ on the rotation melt rheometer less than 30,000 pools.

39. the polymer blend of claim 1, wherein said polyester is 170 ℃ of hypocrystalline times that have greater than 5 minutes.

40. the polymer blend of claim 1, wherein said polyester is 170 ℃ of hypocrystalline times that have greater than 50 minutes.

41. the polymer blend of claim 1, wherein said polymer blend is 23 ℃ of density that have less than 1.2g/ml.

42. the polymer blend of claim 1, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product.

43. the polymer blend of claim 1, wherein said polyester according to the yellowness index of ASTM D-1925 less than 50.

44. the polymer blend of claim 1, wherein said polyester have 23 ℃ according to ASTM D256 with 1/8 inch thick band sample in the notched izod impact strength of the 10ft-lbs/in at least that measures of 10 mil breach.

45. the polymer blend of claim 1, wherein said polyester comprises the residue of at least a catalyzer, this catalyst pack sn-containing compound or its reaction product.

46. comprise the manufacturing goods of the polymer blend of claim 1.

47. comprise the manufacturing goods of the polymer blend of claim 1, wherein said polyester have 23 ℃ according to ASTM D256 with 1/8 inch thick band sample in the notched izod impact strength of the 3ft-lbs/in at least that measures of 10 mil breach.

48. comprise the manufacturing goods of the polymer blend of claim 1, wherein said polyester have 23 ℃ according to ASTM D256 with 1/4 inch thick band sample in the notched izod impact strength of the 10ft-lbs/in at least that measures of 10 mil breach.

49. comprise film or thin plate according to the polymer blend of claim 1.

50. polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 15-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-85mol%;

Wherein total mol% of dicarboxylic acid component be 100mol% and

Total mol% of diol component is 100mol%;

Wherein said polyester concentration with 0.25g/50ml in 60/40 (wt/wt) phenol/tetrachloroethane is 0.5-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration; And

Wherein said polyester has 85-130 ℃ Tg.

51. the polymer blend of claim 50, wherein said logarithmic viscosity number are 0.5-0.75dL/g.

52. the polymer blend of claim 50, wherein said logarithmic viscosity number are 0.60-0.72dL/g.

53. the polymer blend of claim 50, wherein said logarithmic viscosity number are 0.6-0.75dL/g.

54. the polymer blend of claim 50, wherein said logarithmic viscosity number are 0.60-0.72dL/g.

55. the polymer blend of claim 50, the diol component of wherein said polyester comprises 2,2,4 of 15-25mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 75-85mol%.

56. the polymer blend of claim 50, the diol component of wherein said polyester comprises 2,2,4 of 17-28mol%, 4-tetramethyl--1, the cyclohexanedimethanol of 3-cyclobutanediol and 72-83mol%.

57. the polymer blend of claim 50, wherein said polyester has 95-125 ℃ Tg.

58. the polymer blend of claim 50, wherein said polyester has 95-120 ℃ Tg.

59. the polymer blend of claim 50, wherein said polyester has 95-115 ℃ Tg.

60. the polymer blend of claim 50, wherein said polyester has 100-120 ℃ Tg.

61. polymer blend comprises at least a polyester, this polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%; With

(c) residue of at least a branching agent;

Wherein total mol% of dicarboxylic acid component be 100mol% and

Total mol% of diol component is 100mol%; With

Wherein said polyester has 85-130 ℃ Tg.

62. polymer blend comprises:

(I) at least a polyester comprises:

(a) dicarboxylic acid component comprises:

I) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

I) 2,2,4 of 10-30mol%, 4-tetramethyl--1,3-cyclobutanediol residue; With

The ii) cyclohexanedimethanol residue of 70-90mol%; With

(II) at least a thermo-stabilizer or its reaction product;

Wherein total mol% of dicarboxylic acid component be 100mol% and

Total mol% of diol component is 100mol%;

Wherein the concentration with 0.25g/50ml is 0.35-1.2dL/g in the logarithmic viscosity number of 25 ℃ of mensuration in 60/40 (wt/wt) phenol/tetrachloroethane; With

Wherein said polyester has 85-130 ℃ Tg.

63. the composition of claim 1, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it is selected from least a of phosphoric acid, phosphorous acid, phosphonic acids, phospho acid, phosphonous acid and various ester and salt.

64. the composition of claim 63, wherein said ester are selected from least a of alkyl, branched-alkyl, substituted alkyl, two sense alkyl, alkyl oxide, aryl and substituted aryl ester.

65. the composition of claim 62, wherein said polymer blend comprises at least a thermo-stabilizer or its reaction product, it is selected from least a thermo-stabilizer, and this thermo-stabilizer is selected from least a of replacement or unsubstituted alkyl phosphate, replacement or unsubstituted aryl phosphate, replacement or unsubstituted mixed phosphate alkyl aryl ester, diphosphites, phosphoric acid salt, phosphine oxide and blended aryl phosphite alkyl ester.

66. the composition of claim 62, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it is selected from least a of alkyl phosphate, aryl phosphate, blended alkyl aryl phosphate, its reaction product and composition thereof.

67. the composition of claim 62, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it is selected from least a aryl phosphate.

68. the composition of claim 62, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it is selected from least a triaryl phosphate.

69. the composition of claim 62, wherein said polymer blend comprises at least a alkyl phosphate.

70. the composition of claim 62, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it comprises following at least a: diphosphites, phosphoric acid salt, phosphine oxide and blended aryl phosphite alkyl ester.

71. the composition of claim 62, wherein said polymer blend comprise at least a thermo-stabilizer or its reaction product, it comprises phosphorus atom.

72. the polymer blend of claim 1, wherein said polyester is unbodied.

73. comprise the manufacturing goods of the polymer blend of claim 1.

74. comprise film or thin plate according to the polymer blend of claim 1.

75. the goods of claim 1, wherein said manufacturing goods are formed by extrusion blow molded.

76. the goods of claim 75, wherein said manufacturing goods are formed by crowded base stretch-blow.

77. the goods of claim 73, wherein said manufacturing goods are formed by injection moulding.

78. the goods of claim 73, wherein said manufacturing goods are formed by injection stretch blow.

79. according to the film or the thin plate of claim 74, wherein said film or thin plate are produced by extrusion molding or calendering.

80. comprise injection-molded item according to the polymer blend of claim 1.

81. a blend comprises:

(a) polyester of at least a claim 1 of 5-95wt%; With

(b) at least a polymeric constituent of 5-95wt%.

82. the blend of claim 81, wherein said at least a polymeric constituent are selected from following at least a: nylon; The polyester that is different from the polyester of claim 1; Polymeric amide; Polystyrene; Polystyrene copolymer; Styrene acrylonitrile copolymer; Acrylonitrile butadient styrene; Polymethylmethacrylate; Acrylic copolymer; Polyetherimide; Polyphenylene oxide is as poly-(2,6-dimethyl phenylate); Or polyphenyl ether/styrene blend; Polyphenylene sulfide; Polyphenylene sulfide/sulfone; Poly-(ester-carbonic ether); Polycarbonate; Polysulfones; Polysulfones ether; Poly-(ether-ketone) with aromatic dihydroxy compound.

83. one kind is used to prepare claim 1,50,61 and 62 each the method for polyester, comprises the following steps:

(a) dicarboxylic acid component comprises:

(i) terephthalic acid residue of 70-100mol%;

(b) diol component comprises:

(i) 2,2,4,4-tetramethyl--1,3-cyclobutanediol residue; With

(ii) cyclohexanedimethanol residue;

84. adding in step (II), the method for claim 83, wherein said thermo-stabilizer replace in step (I), adding.

85. the method for claim 83, wherein said thermo-stabilizer are added in step (I) with (II).

86. adding afterwards in step (II), the method for claim 83, wherein said thermo-stabilizer replace in step (I), adding.